Persistent Organochlorine Residues in Livers of Six Species of Ciconiiformes (Aves) from Spain

Liver samples of 42 birds belonging to 6 species of Ciconiiformes (grey heron (n = 17), little egret (n = 12), cattle egret (n = 1), glossy ibis (n = 1), little bittern (n = 1), and white stork (n = 10)), collected from two different zones of Spain (Ebro Delta and Madrid) in 1992–1997, were analyzed for organochlorine pesticides and PCBs. ΣPCBs (sum of concentrations of individual congeners), p,p′-DDE, HCB, γ-HCH, and heptachlor epoxide were the most prevalent residues detected in all samples (occurrence > 95%). There were no statistically significant differences in organochlorine levels between grey herons and little egrets, while levels of ΣPCBs, p,p′-DDE, HCB, γ-HCH, and heptachlor were significantly lower for white storks. These results could be explained by the different habitat of these species, aquatic in the Ebro Delta (grey herons, little egrets) and dry in Madrid (white stork), and their diverse feeding habits.     

Role of extracellular compounds in Cd-sequestration relative to Cd uptake by bacterium Sinorhizobium meliloti

The role of bacterially derived compounds in Cd(II) complexation and uptake by bacterium Sinorhizobium meliloti wild type (WT) and genetically modified ExoY-mutant, deficient in exopolysaccharide production, was explored combining chemical speciation measurements and assays with living bacteria. Obtained results demonstrated that WT- and ExoY-strains excreted siderophores in comparable amounts, while WT-strain produced much higher amount of exopolysaccharides and less exoproteins. An evaluation of Cd(II) distribution in bacterial suspensions under short term exposure conditions, showed that most of the Cd is bound to bacterial surface envelope, including Cd bound to the cell wall and to the attached extracellular polymeric substances. However, the amount of Cd bound to the dissolved extracellular compounds increases at high Cd(II) concentrations. The implications of these findings to more general understanding of the Cd(II) fate and cycling in the environment is discussed.     

Synthesized magnetic nanoparticles coated zeolite for the adsorption of pharmaceutical compounds from aqueous solution using batch and column studies

The contamination of fresh water with pharmaceutical and personal care products (PPCPs) has risen during the last few years. The adsorption of some PPCPs namely, Diclofenac-Na, Naproxen, Gemfibrozil and Ibuprofen from aqueous solution has been studied, magnetic nanoparticles coated zeolite (MNCZ) has been used as the adsorbent. Batch adsorption experiment was conducted to study the influences of different adsorption parameters such as contact time, solution pH and PPCPs concentrations in order to optimize the reaction conditions. The removal was favored at low pH values. Thus, as pH turns from acidic to basic conditions these compounds were less efficiently removed. The initial concentration does not appear to exert a noticeable effect on the removal efficiency of the studied PPCPs at low concentrations, but it showed less removal efficiency during high concentration of PPCPs especially for Ibuprofen. The removal of Diclofenac-Na was independent on time, while the contact time was of significant effect on the adsorption of Naproxen, Gemfibrozil and Ibuprofen even though these compounds were removed up to 95% during 10 min using MNCZ. From the isotherm adsorption study, the adsorption of PPCPs studied on MNCZ was best fitted with Freundlich isotherm equation. Pseudo-second order model providing the best fit model with the experimental data. Column adsorption study was conducted to compare the removal efficiency of MNCZ with other processes used at drinking water treatment plants (DWTPs), MNCZ showed high removal efficiency (>99%) than other used processes at DWTPs.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Chemical composition and antimicrobial activities of the essential oil from the seeds of Enterolobium contortisiliquum (leguminosae)

Seeds of Enterolobium contortisiliquum were subjected to steam distillation to obtain a light yellow essential oil in a yield of 3 ml/kg of seeds. The major components of the oil were identified using gas chromatography/mass spectrometry (GC-MS) and were furfural, limonene, linalool, estragole, carvone, and apiole with carvone representing more than 50% of the total composition. Antimicrobial activities of the essential oil were determined against four species of gram positive bacteria (Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Micrococcus luteus) and two gram negative bacteria (Klebsiella pneumoniae, Serratia Marcescencs). The essential oil inhibited the growth of all tested bacteria but was most effective against the gram positive bacteria. Chemicals that are responsible for the antibacterial effect of the essential oil were determined using the bio-autography thin layer chromatography (TLC) technique. The active compounds responsible for the activity were found to be carvone and estragole.     

COMPARISON BETWEEN SOLID–PHASE EXTRACTION METHODS FOR THE CHROMATOGRAPHIC DETERMINATION OF ORGANOPHOSPHORUS PESTICIDES IN WATER

A solid-phase microextraction (SPME) procedure has been developed to ex tract eight organophosphorus pesticides (OPs) in water and the method was compared with a conventional solid phase extraction (SPE) technique. The extracted OPs were analyzed by gas chromatography using thermionic specific detection. Both extraction methods presented linear calibration at least over the concentration range investigated (100 to 1000 ng.mL^?1 for SPE and 1 to 100 ng.mL^?1 for SPME). SPME method presented higher sensitivity than SPE. The quantitation limits were between 0.1 to 1.0 ng.mL^?1 for SPME depending upon the analyte, and 100 ng.mL^?1 for SPE. The precision, as measured by the standard deviations (RSD), were in the range 3.6 % to 5.8 % for SPME and 2.4 % to 9.2 % for SPE.

Along with the feature of being a solvent – free sampling technique, SPME offers additional benefits due to its high sensitivity, simplicity, and small size sample required (typically: SPE – 500 mL, SPME – 5 mL).     

Insight into fluorescence properties of 14 selected toxic single-ring aromatic compounds in water: Experimental and DFT study

• The fluorescence peak location of 14 compounds interpreted at protein-like region. • The p-electron system inside aromatic ring contributes to the fluorophore region. • Functional group variation effects the emission spectra. • Decrease in quantum yield and increase in DE is due to atomic weight F>Cl>Br>I. • Theoretically results are in line with experimental ones. Various single-ring aromatic compounds in water sources are of great concern due to its hazardous impact on the environment and human health. The fluorescence excitation-emission matrix (EEMs) spectrophotometry is a useful method to identify organic pollutants in water. This study provides a detailed insight into the fluorescence properties of the 14 selected toxic single-ring aromatic compounds by experimental and theoretical analysis. The theoretical analysis were done with Time-Dependent Density Functional Theory (TD-DFT) and B3LYP/6-31G (d,p) basis set, whereas, Polarizable Continuum Model (PCM) was used to consider water as solvent. The selected compounds displayed their own specific excitation-emission (Ex/Em) wavelengths region, at Ex<280 nm and Em<340 nm, respectively. Whereas the theoretical Ex/Em was observed as, Ex at 240 nm–260 nm and Em at 255 nm–300 nm. Aniline as a strong aromatic base has longer Em (340 nm) than alkyl, carbonyl, and halogens substituted benzenes. The lone pair of electrons at amide substituent serves as a p-electron contributor into the aromatic ring, hence increasing the stability and transition energy, which results in longer emission and low quantum yield for the aniline. The fluorescence of halogenated benzenes illustrates an increase in the HOMO-LUMO energy gap and a decrease in quantum yield associated with atomic size (F>Cl>Br>I). In this study the theoretical results are in line with experimental ones. The understanding of fluorescence and photophysical properties are of great importance in the identification of these compounds in the water.     

Chronic risk assessment of exposure to volatile organic compounds in the atmosphere near the largest Mediterranean industrial site

This study focuses on characterising the risk of exposure to volatile organic compounds (VOCs) by means of inhalation in people living in the vicinity of the largest chemical production site in the Mediterranean area. Eighty-six VOCs were initially selected for this study based on their adverse environmental and health effects. The monitoring campaign was conducted for 276 days in three different locations around the chemical site. The analytical method used for the characterisation was based on European standard method EN-14662-2, which consists of the active sampling of air for 24 h in charcoal tubes, followed by extraction with carbon disulphide and GC-MS analysis. Forty-four VOCs with toxicological data available concerning their carcinogenic and non-carcinogenic health effects were quantified during the monitoring campaign. None of the quantified VOCs showed average concentrations exceeding their chronic reference concentrations and, therefore, no non-carcinogenic health effects are expected as a result of this exposure. However, the global average cancer risk due to VOC exposure in the area (3.3 × 10^− 4) was found to be above the values recommended by the WHO and USEPA.The influence of the analytical method was also evaluated by comparing cancer risk estimates using a thermal desorption (TD) method based on method EN-14662-1. The results of the 24-h samples for the solvent extraction method were compared with the average of 12 daily samples of 2-h for the TD method for 24 sampling days. Although the global estimated lifetime cancer risk was statistically comparable for both methods, some differences were found in individual VOC risks.To our knowledge, this is the first study that estimates the carcinogenic and non-carcinogenic risks posed by the inhalation of VOCs in people living near a chemical site of this size, and compares the estimated cancer risk obtained using two different standard analytical methods.     

三重四极杆质谱技术测定固体废弃物中多氯联苯

以二氯甲烷为萃取剂,采用快速溶剂萃取、凝胶渗透色谱净化、三重四极杆质谱技术测定固体废弃物中7种多氯联苯单体,选择十氯联苯为内标物,2,4,5,6-四氯间二甲苯为替代物。质谱采用MRM扫描,优化了目标物质保留时间、母离子和子离子质量数及碰撞能量等参数。方法在0.050 mg/L～2.00 mg/L范围内线性良好,7种多氯联苯单体的检出限为0.194 ng/g～0.355 ng/g(以称取30 g样品、定容至2.0 mL计),标准样品回收率多在60%～105%之间,空白加标样品测定值的相对标准偏差在8.6%～13.0%之间。     

常州某农药生产场地土壤中挥发性有机物污染状况调查

对常州某农药生产场地土壤中挥发性有机物污染状况进行了调查。数据表明,该场地土壤中挥发性有机物污染以苯系物和卤代烃为主。苯系物浓度为0～56.7mg/kg,卤代烃浓度为0～1.14mg/kg,有潜在风险。