Spectroscopic behavior of oxygenated combustion by-products

The oxygenated species, massively produced in the energy production plants based on combustion processes, constitute one of the most numerous categories of hazardous air pollutants. Therefore, development of real time diagnostic tools are needed in order to study their formation during combustion processes and to reveal their presence both in the exhaust and in the atmosphere. In this work, oxygenated compounds were identified inside fuel-rich premixed ethylene/air flames by means of ultraviolet fluorescence spectroscopy with the support of qualitative chemical analysis of the sampled combustion gases.

Strong band progression, typical of aldehydic functionality, were recognized in fluorescence spectra (λ_exc=355 nm) measured in the early oxidation region of premixed flames varying the equivalence ratio from 3.0 up 21.6. Downstream of the oxidation region, spectroscopic signatures of pyrolytic species were found to prevail on those peculiar of oxygenated compound. The position and the extension of the two main flame zones were found to depend on the flame conditions (C/O ratio) due to the effect of the C/O ratio on the temperature history along the flame axis. This correlation was interpreted on the basis of the measured axial temperature profiles.     

Generation and stability of bentonite colloids at the bentonite/granite interface of a deep geological radioactive waste repository

The possible mechanisms of colloid generation at the near field/far field interface of a radioactive repository have been investigated by means of novel column experiments simulating the granite/bentonite boundary, both in dynamic and in quasi-static water flow conditions. It has been shown that solid particles and colloids can be detached from the bulk and mobilised by the water flow. The higher the flow rate, the higher the concentration of particles found in the water, according to an erosion process. However, the gel formation and the intrinsic tactoid structure of the clay play an important role in the submicron particle generation even in the compacted clay and in a confined system. In fact, once a bentonite gel is formed, in the regions where the clay is contacted with water, clay colloids can be formed even in quasi-static flow conditions. The potential relevance of these colloids in radionuclide transport has been studied by evaluating their stability in different chemical environments. The coagulation kinetics of natural bentonite colloids was experimentally studied as a function of the ionic strength and pH, by means of time-resolved light scattering techniques. It has been shown that these colloids are very stable in low saline (approximately 1 x 10(-3) M) and alkaline (pH > or = 8) waters.     

Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Assessing the effect of climate oscillations and land-use changes on streamflow in the central Spanish Pyrenees

Plans to increase the amount of irrigated land in Mediterranean countries should consider how changes in climate and land-use affect water resources. In this study, both precipitation and temperature were used to analyze regional trends in discharge in the basins of the Central Spanish Pyrenees since the mid-20th century. Annual variations in the relationship between precipitation and discharge suggested that discharge was relatively lower in the second half of the study period, coinciding with major changes in land use. On a monthly scale, precipitation increased significantly in October, April, and July, and decreased in March, and temperature increased in January and February and decreased in April. Nevertheless, discharge has decreased significantly in most months in the past 50 years. Land-use and plant-cover changes are the only nonclimatic factor that can explain the loss of around 30% of the average annual discharge.     

Organochlorine and butyltin residues in walleye pollock (Theragra chalcogramma) from Bering Sea, Gulf of Alaska and Japan Sea

Persistent organochlorine (OC) and toxic butyltin compounds (BTs) were determined in walleye pollock (Theragra chalcogramma) collected from Gulf of Alaska, Bering Sea and Japan Sea, during 1991 and 1992. Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and its metabolites were the most abundant compounds ranging up to 3200 and 2500 ng/g on lipid weight, respectively, followed by chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs) and hexachlorobenzene (HCB) in the liver of walleye pollock. Concentrations of HCHs and HCB in walleye pollock from these remote areas were higher than those in fishes from the western North Pacific and Japanese coastal waters, indicating atmospheric transport of these compounds to higher latitude regions such as Bering Sea and Gulf of Alaska and/or local input around northern Japan Sea. The concentrations of other OCs were generally comparable to those in fishes from North Pacific Ocean and Japanese waters but significantly lower than in cod-like fishes from North Atlantic and European countries. Among sampling locations, walleye pollock from Japan Sea showed higher concentrations of DDTs and HCHs compared to fishes from Bering Sea and Gulf of Alaska, suggesting greater input of these compounds around Japan Sea. Slower declining trend of DDTs and CHLs and an increasing pattern of PCBs concentrations were found in walleye pollock from Bering Sea during 1982-1992. This may imply a continuous input of these compounds by long-range transport and/or long-term persistency in these cold regions. Compared to the fishes from Japan Sea, walleye pollock from Bering Sea and Gulf of Alaska showed higher proportions of alpha-HCH and p,p'-DDE in the composition of HCH isomers and DDT compounds, respectively. This suggests selective transportability of these compounds during long-range transport to higher latitude remote areas. Concentrations of tributyltin (TBT) in the muscle of walleye pollock ranged from 1.1 to 5.5 ng/g on wet weight. Concentrations of TBT in deep-sea walleye pollock from Gulf of Alaska and Bering Sea were lower than those in Japan Sea.     

Bioavailability and biodegradation of prosulfocarb in soil

Active microbial degraders of the herbicide prosulfocarb (PSC) were isolated to evaluate their performance in soil with a view to their use for bioremediation. The isolated cultures (a microbial consortium and a Pseudomonas sp. strain) were active when tested in mineral medium with PSC as the only carbon source, but had an adverse effect on the soil indigenous microflora. Biodegradation in the inoculated soils was thus lower than in the uninoculated soil when only the indigenous microflora was present. Further tests showed that the strong affinity of PSC for soil organic matter affected its bioavailability and hence its biodegradation by the inocula. Bioremediation of PSC contaminated soils could thus be undertaken by biostimulation of indigenous microflora.     

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.     

Radium-226 in cattails, Typha latifolia, and bone of muskrat, Ondatra zibethica (L.), from a watershed with uranium tailings near the city of Elliot Lake, Canada

Radium-226 concentrations were measured in the main food plants (cattails, Typha latifolia) and bone of adult muskrats (Ondatra zibethica (L.)), taken from a study area near Quirke Lake in the Serpent River drainage basin. This watershed receives drainage containing radionuclides from the U tailings near the City of Elliot Lake, Ontario, Canada. Two control sites (one local, one 130 km distant) were also sampled. Radium-226 levels in cattails varied by plant part and place of collection. Roots sampled in the study area had the highest mean (226)Ra level (1135.0 mBq g(-1)), stems and leaves had 284.2 and 275.9 mBq g(-1), respectively (dry-weight basis, n = 6 in all cases). Local and distant control cattails carried much lower (226)Ra levels (20.2 and 15.2 mBq g(-1) dry weight, respectively, using pooled equal portions of all plant parts, n = 3 in both cases). Muskrats from waters with mean total (226)Ra levels in the period, 1984-1987 greater than 75.0 mBq litre(-1) ('study-high' sites), near U tailings within 10 km of Quirke Lake, had a mean (geometric) bone level of (226)Ra of 344.9 mBq g(-1) (dry-weight basis, n = 36); those from nearby waters, containing < 75.0 mBq litre(-1) of (226)Ra ('study-low' sites), had a mean bone level (80.3 mBq g(-1), n = 9) similar to animals taken in unaffected local control areas 20 km from the tailings (79.1 mBq g(-1), n = 12); animals from the distant control area, near Sudbury, Ontario, had the lowest mean burden (11.5 mBq g(-1), n = 24). Levels were unrelated to age or sex of the animals. Dry-weight based (226)Ra concentration ratios (bone concentration/plant tissue concentration) were calculated to range from 0.3-1.4 in the study-high area to 2.4-6.3 in the local control area. Wet-weight based concentration ratios were about 4.3 times higher. Concentration ratios were similar to values calculated for other species and in general agreement with values calculated for humans. The muskrat is judged to be a useful indicator (biomonitor) of environmental (226)Ra levels as there is a highly significant positive correlation coefficient (r = 0.74) between bone and ambient (water) concentrations of the radionuclide (F79 = 95.04, P < 0.0001) Estimated yearly (226)Ra intake by people eating muskrats was calculated to be below the current allowable level set by Canadian regulatory authorities.     

Solvent and surfactant enhanced solubilization, stabilization, and degradation of amitraz

In an effort to help with the development of effective dip vat management and waste disposal strategies this study determined how solution properties such as pH, buffer composition, ionic strength, temperature, solubility in organic solvents and the addition of commonly used solubilizing agents influenced the hydrolysis of amitraz. Amitraz degrade by means of hydrolysis described by a pseudo-first order rate process and a type ABCD pH rate profile. Hydrolysis increased with temperature and was fastest at low pH, slowest at neutral to slightly alkaline pH, and slightly increased above pH 10. However, buffer concentration and ionic strength influenced the hydrolysis rate and had to be accounted for before constructing a pH rate profile. Hydrolysis seems to depend on the dielectric constant of solvent mixtures and was fastest in water, slower in propylene glycol and ethanol solutions, and slowest in DMSO mixtures. In surfactant solutions, anionic micelles enhanced and cationic micelles retarded the hydrolysis rate. The magnitude of micellar effects decreased with increasing concentrations of the surfactants. The increased solubility and faster hydrolysis of amitraz in the sodium lauryl sulfate solutions showed that anionic surfactants potentially could be used for cleaning up amitraz spills, because it both solubilized the drug and catalyzed hydrolysis.