Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods

Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a significant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difficulty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specific PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the filters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Groundwater contamination evolution in the Guadiamar and Agrio aquifers after the Aznalcóllar spill: assessment and environmental implications

In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm³ of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Use of cholinesterase activity in monitoring chlorpyrifos exposure of steer cattle after topical administration

The aim of this work was to study the pharmacokinetic behavior and the inhibitory effect of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities of chlorpyrifos (CPF) in steer cattle after pour-on administration. Determination of cholinesterase activity in plasma and erythrocyte was carried out according to Ellman kinetic method. CPF was analyzed by gas chromatography. AChE was the predominant form of cholinesterase analyzed, with low levels of BChE in plasma. Following the treatment with CPF, the maximum inhibitory effect on AChE or BChE were 50.88 ± 11.57 and 42.66 ± 12.01%, respectively. The chlorpyrifos plasma concentrations observed were low and they presented a high variability. Chlorpyrifos peak plasma concentration (10.42 ± 4.76 μ g/L) was reached at 8.42 ± 13.97 h. The pesticide was not detected in plasma after 48 h post treatment. The values of area under the curve (AUC) were 118.48 ± 87.46 μ g· h/L and mean resistance time (MRT) were 13.38 ± 10.41 h. The pour-on exposure to the organophosphate chlorpyrifos significantly reduced AChE and BChE activity in steer cattle and the recovery was not reached on 50 days post-treatment.     

Studies of methamidophos-C-14 in Costa Rican vegetables and soils

In order to see the effect of time lapse between the last application of methamidophos and harvesting insecticide was applied on lettuce plants (6,84 μCi in one experiment and 4,03 μCi in the other experiment). Analysis of the crops harvested 3 days after last application showed 9,7 ppm residues on leaves, while crops harvested 1 day after application showed residues of 12,7 ppm (25% more). Treatment of tomato plants (39,65 μCi, 1,01 kg/ha) gave residues in fruits 4,92 ppm after 8 days interval between last application and harvesting. 40 days gap between the last application and harvesting leaved residues of 0,7 ppm in fruits which is much less as recommended by FAO/WHO (1 – 2 ppm).Degradation of this insecticide is dependent on the matrix of the soil, this breakdown is observed in the first ten days and than after it remains constant. C-14 radioactivity extracted from soil and plant analysis was methamidophos (92%)     

Prediction of particulate loading in exhaust from fabric filter baghouses with one or more failed bags

Loss of filtration efficiency in a fabric filter baghouse is typically caused by bag failure, in one form or another. The degree of such failure can be as minor as a pinhole leak or as major as a fully involved baghouse fire. In some cases, local air pollution regulations or federal hazardous waste laws may require estimation of the total quantity of particulate matter released to the environment as a result of such failures. In this paper, a technique is presented for computing the dust loading in the baghouse exhaust when one or more bags have failed. The algorithm developed is shown to be an improvement over a previously published result, which requires empirical knowledge of the variation in baghouse pressure differential with bag failures. An example calculation is presented for a baghouse equipped with 200 bags. The prediction shows that a small percentage of failed bags can cause a relatively large proportion of the gas flow to bypass the active bags, which, in turn, leads to high outlet dust loading and low overall collection efficiency from the baghouse.     

Perfluorinated chemicals in selected residents of the American continent

Perfluorinated chemicals (PFCs) are used in multiple consumer products. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the most widely studied PFCs, may be potential developmental, reproductive, and systemic toxicants. Although PFCs seem to be ubiquitous contaminants found both in humans and animals, geographic differences may exist in human exposure patterns to PFCs. We measured 11 PFCs in 23 pooled serum samples collected in the United States from 1990 through 2002, and in serum samples collected in 2003 from 44 residents from Trujillo, Peru. PFOS and PFOA were detected in all the pooled samples; perfluorohexane sulfonic acid (PFHxS) was detected in 21. Median concentrations were 31.1 micrograms per liter (mug/l, PFOS), 11.6 microg/l (PFOA), and 2 microg/l (PFHxS). The 90th percentile concentrations of PFCs in the 44 Peruvian residents were 0.7 microg/l (PFOS), 0.1 microg/l (PFOA), and <0.3 microg/l (PFHxS). The frequencies of detection were 20% (PFOS), 25% (PFOA), and 9% (PFHxS). The frequent detection of selected PFCs in the pooled samples from the United States and the lack of clear concentration trends based on a year of collection suggest a sustained widespread exposure to these compounds among US residents, at least since the 1990s. By contrast, the much lower frequency of detection and concentration ranges of PFCs in Peru suggest a lower exposure of Peruvians to PFCs compared with North Americans. Genetic variability, diet, lifestyle, or a combination of all these may contribute to the different patterns of human exposure to PFCs in the United States and Peru.     

Microplastic distribution in surface sediments along the Spanish Mediterranean continental shelf

Environmental Science and Pollution Research - Microplastics (MPs) are widely recognised as a contaminant of emerging concern in the marine environment. This work provides original data of the...