Kinetic effects on the interactions of Rh(III) with humic acids as determined using size-exclusion chromatography (SEC)

The anthropogenic inputs of Rh in the environment—together with other platinum group elements—have increased considerably during the last 20–30 years. However, thermodynamics and kinetics on the interaction of Rh with natural organic and inorganic ligands are still poorly characterized. Here, we report the time-dependent speciation of rhodium chlorides spiked to model freshwater with and without the presence of humic substances. Rhodium species were determined using size-exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). Results indicate that organic matter can effectively bind rhodium, but the extremely slow reaction kinetics of Rh plays a significant role on its speciation in natural waters. Accordingly, formation of Rh-organic complexes from spiked rhodium chlorides required around 15 days to reach equilibrium; this should be taken into account in those laboratory experiments where the biological interactions of Rh, using spiked samples, are studied. Regarding Rh inorganic speciation in freshwater, the available thermodynamic constants predict the dominance of the neutral trihydroxo and negatively charged tetrahydroxo rhodium complexes over typical pHs (6–8); our results, however, indicate only the presence of negatively charged hydroxocomplexes at pH 7. Reexamination of the Rh stability constants suggest that these hydroxylated rhodium complexes may also dominate its inorganic speciation in seawater.     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.     

Climate change influence on POPs distribution and fate: a case study

Climate change has the potential of affecting the behaviour and distribution of organic pollutants, including POPs. Direct effects of climate change, like temperature increase, modification of wind and precipitation patterns, sea level rise, snow and ice cover, may be very effective in altering the partitioning of POPs among the environmental compartments. Other consequences of future climate scenarios may imply the alteration of degradation rates, soil properties (and hence land use), air-particle partitioning of chemicals and so forth. A case study is here presented to illustrate the major implications of climate change on the long term at the local scale. A dynamic multimedia model was applied to selected PCB and PCDD/F congeners to simulate the effects of climate change on their distribution and fluxes over the next 50 y in the Venice Lagoon (Italy). Different climate change scenarios were tested, finding noticeable variations in POPs concentration even for minor environmental changes. PCBs and PCDFs environmental concentrations may differ by a factor two in a moderate climate change scenario, compared to a situation with stable climate over the next 50 y. However, model results also suggest that if global warming may have the potential of reducing the environmental levels of these chemicals, it would probably enhance their mobility and hence their potential for long range atmospheric transport.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Assessing supercritical fluid extraction for the analysis of fipronil, kresoxim-methyl, acrinathrin, and pyridaben residues in melon

An analytical method, using supercritical fluid extraction (SFE), was assessed for residue analysis of the insecticides fipronil, acrinathrin and pyridaben and the fungicide kresoxim-methyl in melons. Extraction conditions were optimized on glass beads, as inert material, evaluating different pressures, temperatures, and CO(2) volumes. Also, the extractability of pesticides from hydromatrix and anhydrous magnesium sulfate was evaluated. Both adsorbents were evaluated for the preparation of SFE-spiked melon samples. Extractions of fortified samples were done using 20 mL of CO(2), 300 atm, and 50 degrees C. Different extraction conditions, including the addition of water and methanol as a static modifier, were used to assess the extractability of these pesticides, and the addition of methanol was demonstrated to improve the extraction of all the studied pesticides.     

Development of cleaner-burning brick kilns in Ciudad Juarez, Chihuahua, Mexico

The following results provide a comparison between net airborne contamination produced by the traditional form of kiln used in Northern Mexico and by those modified according to a design by Dr. Robert Marquez. What has become known as the MK style kiln was intended to significantly reduce contaminant emissions. The concept involves covering the kiln with a dome and channeling the output of an active kiln through a second, identical loaded kiln for its additional filtration of the effluents. Kilns of a pair are connected via clay brick channels. The roles are reversed after the initial kiln is refilled. Significant reductions in the particulate and gaseous emissions were achieved in the prototype system, but a connectional problem with recent kiln pairs has also limited the degree of operational success. The problem did not mask the potential of the MK kiln, as will be shown. Additional anticipated benefits to the owners of MK kilns, such as reduced operating cycles and decreased quantities of fuel, also have been verified. Key measurements made during all of the burns were of aerosol densities and buoyancies in the flues, kiln temperatures, and, on a number of occasions, chemical analyses of both aerosol and gaseous effluents. Continuous time histories of aerosol densities for most burns (of a total of -40) provide a basis for examining features and the effects of differing styles of operation with respect to burn efficiency and net contaminant masses. Covering the active kiln with a dome produces a net reduction in dry aerosol effluent mass of a factor between 5 and 10, whereas the addition of a filter kiln produces a net reduction of about a factor of 2. The use of used motor oil as a fuel further reduced aerosol contamination by -1 order of magnitude.     

Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain)

The partitioning of alkylphenols in the dissolved and particulate matter of influents, effluents, accumulation onto sludge and the impact of sewage treatment plant upon receiving waters was studied along the Ter River basin (Catalonia, NE Spain). A solid-phase extraction or pressurized liquid extraction followed by liquid chromatography-mass spectrometry was developed and permitted to determine target compounds with high efficiency in waters, particulate material and sludge. Nonylphenol mono- and diethoxylate, nonylphenol and octylphenol partitioned preferably upon particulate matter and sludge, whereas long chain NPE(3-15)O prevailed in the dissolved phase and was released by effluents. Within the treatment process, a net accumulation of alkylphenols in sludge was found, producing up to 148g/t/month. The removal efficiency of alkylphenols was of 37-90% and depended on the treatment. Assessment on the fate of these contaminants within STPs is discussed in terms of flow rates, biological oxygen demand and tons of sludge produced.     

Design of a model to assess the environmental risk of leachate dams

Leachate dams store very toxic liquids, leachate, that contain a large amount of pollutant substances. Most of them are located in gullies or ravines, so if a dam breaks, leachate would advance downstream provoking an important environmental impact. In order to assess this environmental risk, the following procedure has been established: firstly, rating curves have been set up which relate characteristics of the dam with the environmental risk, secondly, a weight has been assigned to each parameter, and thirdly, the environmental elements which could be affected by the leachate have been assessed. Relating the risk generated by the characteristics of the dam with the environmental elements located in the risk area, the environmental risk index of a leachate dam can be calculated. If the environmental risk index exceeds a certain value, then it is a dam with a high environmental risk. A high value can be due to low geotechnical stability, to very sensitive environmental elements, or both.     

Field derived accumulation and release kinetics of DDTs in plants

Vegetation plays an important role in influencing the air/surface exchange of semivolatile organic compounds (SOCs). In order to predict the capability of different plant species to capture chemicals from the air, plant-air partition coefficients and kinetic accumulation parameters must be defined. In this study, potted plants of three different species were transferred to the vicinity of a source point for DDT, namely a contaminated area around a former production plant in Italy. Leaves were constantly sampled in order to follow the uptake from air over time. Later, the potted plants were transported to a location characterized by background diffuse air concentrations for the release phase. Coupling the experimental results with a two-compartment accumulation model it was possible to derive the kinetics parameters and the plant-air partition coefficient K(PA) for p,p'-DDT. The logK(PA) (on a mass/volume basis) ranged between 1.7 and 2.2 for the different species. The uncertainties related to the different phenomena involved in a field uptake/release experiment are discussed.     

Adaptation of the chlorophycean Dictyosphaerium chlorelloides to stressful acidic, mine metal-rich waters as result of pre-selective mutations

Several species of microalgae, closely related to mesophilic lineages, inhabit the extreme environment (pH 2.5, high levels of metals) of the Spain's Aguas Agrias Stream water (AASW). Consequently, AASW constitutes an interesting natural laboratory for analysis of adaptation by microalgae to extremely stressful conditions. To distinguish between the pre-selective or post-selective origin of adaptation processes allowing the existence of microalgae in AASW, a Luria-Delbrück fluctuation analysis was performed with the chlorophycean Dictyosphaerium chlorelloides isolated from non-acidic waters. In the analysis, AASW was used as selective factor. Preselective, resistant D. chlorelloides cells appeared with a frequency of 1.1 x 10(-6) per cell per generation. AASW-resistant mutants, with a diminished Malthusian fitness, are maintained in non-extreme waters as the result of a balance between new AASW-resistant cells arising by mutation and AASW-resistant mutants eliminated by natural selection (equilibrium at c. 12 AASW-resistants per 10(7) wild-type cells). We propose that the microalgae inhabiting this stressful environment could be the descendents of chance mutants that arrived in the past or are even arriving at the present.