Comparative study of the oxidation of atrazine and acetone by H2O2/UV, Fe(III)/UV, Fe(iii)/H2O2/UV and Fe(II) or Fe(III)/H2O2

In this study, the rates of degradation of organic compounds by several AOPs (H₂O₂/UV, Fe(III)/UV, Fe(III)/H₂O₂/UV, Fe(II)/H₂O₂ and Fe(III)/H₂O₂) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]_o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H₂O₂/UV. Photo-Fenton process (Fe(III)/H₂O₂/UV) was found to be more efficient than H₂O₂/UV and Fe(II)/H₂O₂ for the mineralization of acetone ([Acetone]_o = 1 mM).     

Preparation of mercury emissions inventory for eastern North America

Point and area inventories of anthropogenic mercury emissions documented by US and Canadian environmental agencies have been aggregated into a single archive for analysis and air pollution modeling work. For 5341 point sources and 1634 aggregated area sources, mercury emissions are apportioned among elemental gaseous [Hg(0)], reactive gaseous[Hg(II)], and particulate [Hg(p)] emissions using speciation factors derived from available monitoring measurements. According to this inventory, 4.82 x 10(5) mol of mercury were emitted in calendar year 1996 in the latitude range 24-51 degrees north, and longitude range 64-91 degrees west, which covers most of North America east of the Mississippi River. Using speciation factors consistent with past emission source studies, we find the relative emission proportions among Hg(0):Hg(II):Hg(p) species are 47:35:18. Maps of the various mercury species' emissions patterns are presented. Gridded emission patterns show local mercury emission extremes associated with individual cement production and municipal incineration facilities, and in contrast to past inventories, population centers do not stand out. Considerable uncertainties are still present in estimating emissions from large point sources, as are methods of apportioning emissions among various mercury species.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO2) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography-electron capture detector (GC-ECD) indicated that the herbicide trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid-phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low-cost home-made system that did not require the use of organic solvents.     

Intercomparison of reactive transport models applied to UO2 oxidative dissolution and uranium migration

Oxidative dissolution of uranium dioxide (UO₂) and the subsequent migration of uranium in a subsurface environment and an underground waste disposal have been simulated with reactive transport models. In these systems, hydrogeological and chemical processes are closely entangled and their interdependency has been analyzed in detail, notably with respect to redox reactions, kinetics of mineralogical evolution and hydrodynamic migration of species of interest.Different codes, where among CASTEM, CHEMTRAP and HYTEC, have been used as an intercomparison and verification exercise. Although the agreement between codes is satisfactory, it is shown that the discretization method of the transport equation (i.e. finite elements (FE) versus mixed-hybrid FE and finite differences) and the sequential coupling scheme may lead to systematic discrepancies.     

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.     

Sustainable watershed management: an international multi-watershed case study

Global freshwater resources are being increasingly polluted and depleted, threatening sustainable development and human and ecosystem health. Utilizing case studies from 4 different watersheds in the United States, Japan, Switzerland, and Brazil, this paper identifies the most relevant sustainability deficits and derives general vectors for more sustainable water management. As a consequence of the demographic and economic developments experienced in the last few decades, each watershed has suffered declines in water quality, streamflow and biotic resources. However, the extent and the cultural perception of these water-related problems vary substantially in the different watersheds, leading to specific water-management strategies. In industrialized countries, exemplified by the US, Switzerland, and Japan, these strategies have primarily consisted of finance- and energy-intensive technologies, allowing these countries to meet water requirements while minimizing human health risks. But, from a sustainability point of view, such strategies, relying on limited natural resources, are not long-term solutions. For newly industrialized countries such as Brazil, expensive technologies for water management are often not economically feasible, thus limiting the extent to which newly industrialized and developing countries can utilize the expertise offered by the industrialized world. Sustainable water management has to be achieved by a common learning process involving industrialized, newly industrialized, and developing countries, following general sustainability guidelines as exemplified in this paper.     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

Topsoil (0-5 cm) composition in eight arctic catchments in northern Europe (Finland, Norway and Russia)

Frozen topsoil samples (0-5 cm) were collected during March/April 1994 in eight Arctic catchments in northern Europe (four in Russia, three in Finland, one in Norway), at different distances and in different wind directions from the emissions of the Russian mining, roasting and smelting industry on the Kola Peninsula. Between 14 and 25 sites were sampled in each of the eight catchments ranging in size from 12 to 35 km2. Results show that close to the smelters in Monchegorsk and Nikel, topsoil is clearly enriched in Ag, As, Bi, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sb, Se, Te and V. Cu and Ni median contents in topsoils collected close to Monchegorsk are about 600 times higher than in the Finnish catchments. The effect of open-cast mining and waste dumps of alkaline rocks from the nephelinite industry near Kirovsk can be seen in the elevated contents of Al, Ba, K, La, Mn, Na, Sr, Ti, Y and Zn in topsoil collected in a nearby catchment. For many elements, however, variations observed in single catchments are as great as the total regional variation. Several elements (e.g. Cd, Hg, Cu, Ni, Pb, S, Zn) show strong positive correlation between the organic content of the sample and the element content observed. Thus it is necessary to determine the organic content of the samples and correct the element levels when using depth-related soil samples (here, the 0-5 cm topsoil layer) for regional mapping.     

First Detection of Hepatitis E Virus in Shellfish and in Seawater from Production Areas in Southern Italy

Shellfish samples (n = 384) from production areas, water samples from the same areas (n = 39) and from nearby sewage discharge points (n = 29) were analyzed for hepatitis E virus (HEV) by real-time and nested RT-PCR. Ten shellfish samples (2.6%) and five seawater samples (12.8%) tested positive for HEV; all characterized strains were G3 and showed high degree of sequence identity. An integrated surveillance in seafood and waters is relevant to reduce the risk of shellfish-associated illnesses.