Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

Biofilm responses to marine fish farm wastes

The changes in the biofilm community due to organic matter enrichment, eutrophication and metal contamination derived from fish farming were studied. The biofilm biomass, polysaccharide content, trophic niche and element accumulation were quantified along an environmental gradient of fish farm wastes in two seasons. Biofilm structure and trophic diversity was influenced by seasonality as well as by the fish farm waste load. Fish farming enhanced the accumulation of organic carbon, nutrients, selenium and metals by the biofilm community. The accumulation pattern of these elements was similar regardless of the structure and trophic niche of the community. This suggests that the biofilm communities can be considered a reliable tool for assessing dissolved aquaculture wastes. Due to the ubiquity of biofilms and its wide range of consumers, its role as a sink of dissolved wastes may have important implications for the transfer of aquaculture wastes to higher trophic levels in coastal systems.     

Long Term Trends in Concentration of Major Pollutants (SO<Subscript>2</Subscript>, CO,NO, NO<Subscript>2</Subscript>, O<Subscript>3</Subscript> and PM<Subscript>10</Subscript>) in Prague – Czech Republic (Analysis of Data Between 1992 and 2005)

To assess the effect of changes in traffic density and fuels used for heating at the beginning of the 1990s, 1992–2005 monthly averages of PM₁₀, SO₂, NO₂, NO, CO and O₃ from Prague, the Czech capital, were analyzed together with long term trends in emissions of major pollutants, fuel consumption and number of vehicles registered in Prague. The data from all monitoring stations were retrieved from the database of the state automated monitoring system. Correlation coefficients between ambient monthly averaged temperature and all pollutants of concern showed distinct seasonal trends. The results showed that while SO₂ and to some extent also CO concentrations dropped namely in the first half of the analyzed period (1992–1997) as a result decreased fossil fuel consumption for local heating, the behaviour of other pollutant concentrations followed a different pattern. PM₁₀ concentrations decreased during the beginning of the 1990s but showed a sign of increase after 2000. Concentrations of ozone and NO₂ did not reveal any significant change throughout the whole studied period. It can be concluded that during the studied period traditional urban sources of pollution, such as coal and oil combustion, lost their importance but were simultaneously substituted by pollutants from automotive transport (namely PM and NO₂) making the problem of air quality even worse.     

Observations of Atmospheric Nitrogen and Phosphorus Deposition During the Period of Algal Bloom Formation in Northern Lake Taihu,China

Cyanobacterial blooms in Lake Taihu occurred at the end of April 2007 and had crucial impacts on the livelihood of millions of people living there. Excessive nutrients may promote bloom formation. Atmospheric nitrogen (N) and phosphorus (P) deposition appears to play an important role in algal bloom formation. Bulk deposition and rain water samples were collected respectively from May 1 to November 30, 2007, the period of optimal algal growth, to measure the bulk atmospheric deposition rate, wet deposition rate, and dry deposition rate for total nitrogen (TN; i.e., all species of nitrogen), and total phosphorus (TP; i.e., all species of phosphorus), in northern Lake Taihu, China. The trends of the bulk atmospheric deposition rate for TN and the wet deposition rate for TN showed double peaks during the observation period and distinct influence with plum rains and typhoons. Meanwhile, monthly bulk atmospheric deposition rates for TP showed little influence of annual precipitation. However, excessive rain may lead to high atmospheric N and P deposition rates. In bulk deposition samples, the average percentage of total dissolved nitrogen accounting for TN was 91.2% and changed little with time. However, the average percentage of total dissolved phosphorus accounting for TP was 65.6% and changed substantially with time. Annual bulk atmospheric deposition rates of TN and TP during 2007 in Lake Taihu were estimated to be 2,976 and 84 kg km⁻² a⁻¹, respectively. The results showed decreases of 34.4% and 78.7%, respectively, compared to 2002–2003. Annual bulk deposition load of TN for Lake Taihu was estimated at 6,958 t a⁻¹ in 2007 including 4,642 t a⁻¹ of wet deposition, lower than the values obtained in 2002–2003. This may be due to measures taken to save energy and emission control regulations in the Yangtze River Delta. Nevertheless, high atmospheric N and P deposition loads helped support cyanobacterial blooms in northern Lake Taihu during summer and autumn, the period of favorable algal growth.     

An Assessment of Oil Pollution in the Coastal Zone of Patagonia,Argentina

The Patagonian coast is considered a relatively pristine environment. However, studies conducted along coastal Patagonia have showed hydrocarbon pollution mostly concentrated at ports that have fishing, oil loading, general merchant, and/or tourist activities. A high value of total aliphatic hydrocarbons (TAH) was found at the Rawson fishing port (741 μg/g dw). In other ports with and without petroleum-related activities, hydrocarbon values were approximately 100 μg/g dw. The highest values for TAH and total aromatic hydrocarbons (TArH) were found in Faro Aristizábal, north of San Jorge gulf (1304 and 737 μg/g dw, respectively). This is very likely the result of petroleum-related activities at the Comodoro Rivadavia, Caleta Cordova, and Caleta Olivia ports located within this gulf. In other coastal areas away from potential anthropogenic sources, hydrocarbon values were less than 2 and 3 μg/g dw for TAH and TArH, respectively. This review of published and unpublished information suggests that ports are important oil pollution sources in the Patagonian coast. More detailed studies are needed to evaluate the area affected by port activities, to understand the mechanisms of hydrocarbon distribution in surrounding environments, and to assess bioaccumulation in marine organisms. Despite that some regulations exist to control oil pollution derived from port and docked vessel activities, new and stricter management guidelines should be implemented.     

Phosphates for Pb immobilization in soils: a review

In its soluble ionic forms, lead (Pb) is a toxic element occurring in waters and soils mainly as the result of human activities. The bioavailability of lead ions can be decreased by complexation with various materials in order to decrease their toxicity. Pb chemical immobilization using phosphate addition is a widely accepted technique to immobilize Pb from aqueous solution and contaminated soils. The application of different P amendments cause Pb in soils to shift from forms with high availability to the most strongly bound Pb fractions. The increase of Pb in the residual or insoluble fraction results from formation of pyromorphite Pb₅(PO₄)₃X where X = F, Cl, Br, OH, the most stable environmental Pb compounds under a wide range of pH and Eh natural conditions. Accidental pyromorphite ingestion does not yield bioavailable lead, because pyromorphite is insoluble in the intestinal tract. Numerous natural and synthetic phosphates materials have been used to immobilize Pb: apatite and hydroxyapatite, biological apatite, rock phosphate, soluble phosphate fertilizers such as monoammonium phosphate, diammonium phosphate, phosphoric acid, biosolids rich in P, phosphatic clay and mixtures. The identification of pyromorphite in phosphate amended soils has been carried out by different non destructive techniques such as X-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, X-ray absorption fine structure, transmission electron microscopy and electron microprobe analysis. The effectiveness of in situ Pb immobilization has also been evaluated by selective sequential extraction, by the toxicity leaching procedure and by a physiologically based extraction procedure simulating metal ingestion and gastrointestinal bioavailability to humans. Efficient Pb immobilization using P amendments requires increasing the solubility of the phosphate phase and of the Pb species phase by inducing acid conditions. Although phosphorus addition seems to be highly effective, excess P in soil and its potential effect on eutrophication of surface water, and the possibility of As enhanced leaching remains a concern. The use of mixed treatments may be a useful strategy to improve their effectiveness in reducing lead phyto- and bioavailability.     

Variations between rice cultivars in root secretion of organic acids and the relationship with plant cadmium uptake

To attempt to understand certain mechanisms causing the variations between rice cultivars with regard to Cd uptake and accumulation, pot soil experiments were conducted with two rice cultivars at different levels of Cd, i.e., 0 (the control), 10, 50 mg Cd kg⁻¹ soil. The two rice cultivars differ significantly with regard to Cd uptake and accumulation. Root secretions of low-molecular-weight organic acids (LMWOA) for each treatment were measured with ion chromatography. The results showed that LMWOA concentrations in the soil planted with Shan you 63 (a high soil Cd accumulator) were all higher than those in the soil planted with Wu yun jing 7 (low soil Cd accumulator) at different soil Cd levels, although the magnitudes of the differences varied for individual LMWOA and depend on soil Cd concentrations. For all six LMWOA, there were significant differences at P < 0.05 or < 0.01 levels for soils treated with 10 and 50 mg kg⁻¹ Cd. The magnitude of the differences was greater under soil Cd treatments, especially at relatively low levels (for example, 10 mg Cd kg⁻¹ soil), than in the control. Acetic acid and formic acid constituted more than 96% of the total concentration of the six LMWOA, while citric acid constituted only about 0.1%. The rice cultivar with higher concentrations of LMWOA in soil accumulated more Cd in the plants. The results indicate that LMWOA secretion by rice root, especially in Cd-contaminated soils, is likely to be one of the mechanisms determining the plant Cd uptake properties of rice cultivars.     

A review of the distribution of particulate trace elements in urban terrestrial environments and its application to considerations of risk

We review the evolution, state of the art and future lines of research on the sources, transport pathways, and sinks of particulate trace elements in urban terrestrial environments to include the atmosphere, soils, and street and indoor dusts. Such studies reveal reductions in the emissions of some elements of historical concern such as Pb, with interest consequently focusing on other toxic trace elements such as As, Cd, Hg, Zn, and Cu. While establishment of levels of these elements is important in assessing the potential impacts of human society on the urban environment, it is also necessary to apply this knowledge in conjunction with information on the toxicity of those trace elements and the degree of exposure of human receptors to an assessment of whether such contamination represents a real risk to the city’s inhabitants and therefore how this risk can be addressed.     

Rapid assessment of different oxygenic phototrophs and single-cell photosynthesis with multicolour variable chlorophyll fluorescence imaging

We present a new system for microscopic multicolour variable chlorophyll fluorescence imaging of aquatic phototrophs. The system is compact and portable and enables microscopic imaging of photosynthetic performance of individual cells and chloroplasts using different combinations of blue, green, red or white light. Automated sequential exposure of microscopic samples to the three excitation colours enables subsequent deconvolution of the resulting fluorescence signals and colour marking of cells with different photopigmentation, i.e., cyanobacteria, green algae, red algae and diatoms. The photosynthetic activity in complex mixtures of phototrophs and natural samples can thus be assigned to different types of phototrophs, which can be quantified simultaneously. Here, we describe the composition and performance of the new imaging system and present applications with both natural phytoplankton and microalgal culture samples.     

Photo-polymerization of triclosan in aqueous solution induced by ultraviolet radiation

The formation of 2,8-dichlorodibenzo-p-dioxin and other harmful degradation products in the photo-degradation process of triclosan is of increasing concern. Here we worked on the identification of polymerized products at high triclosan concentration and on the mechanism of photoreaction. Five dimmers and two trimers of triclosan were detected by liquid chromatography-mass spectrum analysis. 2,8-dichlorodibenzo-p-dioxin was also identified by comparing with an authentic standard. Relatively low pH and high concentration favored the polymerization of triclosan. Three main routes of photoreaction were postulated, namely dechlorination, ring closure and polymerization.