Polychlorinated biphenyls in contaminated soil samples evaluated by GC-ECD with dual-column and GC-HRMS

We present and compare results obtained from the analysis of polychlorinated biphenyls (PCBs) of a limited number of contaminated soil samples collected in three areas of Basilicata region (south of Italy). The levels of PCBs were evaluated by using two analytical methods: (i) parallel dual-column gas-chromatography with dual electron capture detectors (GC-ECD) and (ii) gas-chromatography coupled to high-resolution mass spectrometry (GC-HRMS) via electron impact ionization (EI) in the multiple ion monitoring mode (MIM, two ions per compound). Two extraction methods prior to sample cleanup were also examined: microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE). The MAE was the extraction procedure adopted using acetone/n-hexane (1:1, v/v) as it is mainly characterized by higher sample throughput and allowed reduced consumption of organic solvents. While extraction and analysis of spiked soil samples showed the applicability of both methods, systematic differences between the results were obtained for the sum of PCBs as a result of some non-detected congeners by GC-ECD compared with GC-HRMS. Indeed, high resolution MS using EI mode (electron energy 40eV) with a resolving power of 10,000 provides additional information about the contamination pattern. The GC-ECD screening of 11 soil samples led to just one sample non-compliant to as it was close to the guide value for soils fixed by the Italian legislation (i.e., 60ppb for private or urban soil). Using GC-HRMS, the amount of all PCBs found ranged from 5.4 to 127ppb with five soil samples non-compliant to the guide value. The number of identified congeners ranged from 1 to 9 and 9 to 18 using dual-column GC-ECD and GC-HRMS, respectively.     

Dissipation of terbuthylazine,metolachlor, and mesotrione in soils with contrasting texture

ABSTRACT

This study evaluates the dissipation of terbuthylazine, metolachlor, and mesotrione at different depths in soils with contrasting texture. The field trial was conducted at the Padua University Experimental Farm, north-east Italy. The persistence of three herbicides was studied in three different soil textures (clay soil, sandy soil, and loamy soil) at two depths (0–5 and 5–15 cm). Soil organic carbon content was highest in the clay (1.10%) followed by loam (0.67%) and sandy soil (0.24%); the pH of soils was sub-alkaline. Terbuthylazine, metolachlor, and mesotrione were applied on maize as a formulated product (Lumax®) at a dose of 3.5 L ha^?1. Their dissipation in the treated plots was followed for 2 months after application. The concentrations of herbicides were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine, metolachlor, and mesotrione could be described by a pseudo first-order kinetics. Terbuthylazine showed the highest DT50, followed by metolachlor and mesotrione. Considering the tested soil, the highest DT50 value was found in clay soil for terbuthylazine and metolachlor, whereas for mesotrione there was no difference among soils. Significant differences were found between the two soil depths for terbuthylazine and metolachlor, whereas none were found for mesotrione. These results suggest that soil texture and depth have a strong influence on the dissipation of terbuthylazine and metolachlor, whereas no influence was observed on mesotrione because of its chemical and physical properties.     

Reconstruction of the environmental evolution of a Sicilian saltmarsh (Italy)

The present study deals with the reconstruction of the environmental evolution of a Trapani saltmarsh (southwestern Sicily, Italy) by combining different analytical approaches such as metal content evaluation, low-field nuclear magnetic resonance (NMR) relaxometry, and benthic foraminifera identification. A 41 cm core was collected in the sediments of a Trapani saltmarsh (southwestern Sicily, Italy) at a water depth of about 50 cm. Different time intervals were recognized, each characterized by peculiar features that testify different environmental conditions. In particular, the bottom layers of the sediment core (41–28 cm) comprised the lowest amount of mud fraction, only some selected metals, and the lowest foraminiferal density. Here, co-occurrence of abundant microcrystals of gypsum and Ammonia tepida is indicative of hyper-saline conditions. In the sediments from 28 to 6 cm, mud fraction and number of metal elements resulted higher due to the increase of the anthropogenic pressure. The sediments in the last time interval, corresponding to the environmental recovery of the saltmarsh, showed an increase of foraminiferal density, a decrease of the mud fraction, and a trend in the metal concentration attributable to the protection policy applied since 1990. NMR relaxometry parameters highlighted the changes of sediment chemical–physical heterogeneity going from the bottom to the top of the core. These heterogeneities have been related to the different intervals recognized as aforementioned. The present study highlights how the anthropogenic pressure modifies the environmental conditions of a transitional ecosystem like saltmarshes.     

Prenatal diagnosis of septal agenesis with normal pituitary function

Septal agenesis is a rare brain malformation that is characterized by partial or complete absence of the septum pellucidum, either isolated or associated with other brain anomalies. We report a case presenting with septal agenesis and normal optic chiasm and pituitary function in a fetus at 19 weeks of gestation. Copyright © 2006 John Wiley & Sons, Ltd.     

Adsorption behavior of alpha -cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.     

PCB contamination in farmed and wild sea bass (Dicentrarchus labrax L.) from a coastal wetland area in central Italy

Food consumption is by far the main exposure route for polychlorinated biphenyls (PCBs) for the general population, and fish and fishery products seem to be the main contributors to the total dietary intake of these pollutants. In recent years some investigations have suggested that farmed fish may be more significantly contaminated than wild fish, because of polluted feed. This study measured the levels of PCBs in wild and farmed sea bass (Dicentrarchus labrax L.), one of the most valuable and popular fish in the Italian diet, and assessed the exposure to these pollutants through fish intake. Concentrations of summation operator (Sigma59PCBs) and dioxin-like PCBs (DL-PCBs), as toxic equivalency (TEQ), in fish samples, ranged from 2.2 to 32ngg(-1) and from 0.1 to 4.0pg TEQ((2006) DL-PCBs)g(-1) whole weight, respectively. Farmed sea bass were as average two times more contaminated. Even if the concentrations of DL-PCBs were below the regulation limits, intake of these compounds from nine fish meals per month can in itself exceed the WHO Provisional Tolerable Monthly Intake (PTMI).     

Use of a reactive transport model to describe reductive dechlorination (RD) as a remediation design tool: application at a CAH-contaminated site

In this paper, a numerical model is presented that is capable of describing the complex set of biochemical processes that occur in chlorinated aliphatic hydrocarbon (CAH)-contaminated groundwater when an exogenous electron donor is added. The reactive pattern is based on the degradation pathways of both chlorinated ethanes and ethenes, and it includes electron donor production (H₂ and acetate) from the fermentation of an organic substrate as well as rate-limiting processes related to electron acceptor competition. Coupling of the kinetic model to a convection–dispersion module is described. The calibration phase was carried out using data obtained at a real CAH-contaminated site in the north of Italy. Model simulations of different application scenarios are presented to draw general conclusions on the effectiveness of reductive dechlorination (RD) as a possible cleanup strategy. Early outcomes indicate that cleanup targets can only be achieved if source longevity is reduced. Therefore, metabolic RD is expected to produce beneficial effects because it is known to induce bioenhanced degradation and transformation of CAHs.     

PCDD/Fs and PCBs in ambient air in a highly industrialized city in Northern Italy

Ambient air samples were collected in five locations around a polychlorobiphenyl (PCB) production plant in a highly industrialized city in the north of Italy, for the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and PCBs.PCDD/F atmospheric concentrations were lower than those generally detected in urban areas, while PCB concentrations were higher than in urban and industrialized areas in other countries, especially in the locations closest to the plant. To identify source emissions responsible for air pollution we used principal component analysis (PCA) to compare the “fingerprint” of the air in Brescia with some source-related experimental and published data. This analysis showed that the PCDD/F fingerprints were more similar to steel plant emission data, while none of the PCB air patterns were comparable to emission profiles, indicating that different sources are responsible for the concentration of these two pollutants. The highest PCB concentrations detected in the areas closest to the chemical plant are indicative of its impact on the surrounding environment.     

Influence of environment on insulin sensitivity

Genetic and environmental factors influence insulin sensitivity (IS) during one's lifetime. Actually, uterine environment may affect IS at birth and later in life. In particular, various exogenous toxic substances, coupled to a genetic predisposition, may remarkably influence the regulation of the hypothalamus–hypophysis–adrenal gland axis, and the production or the activity of insulin, cerebral incretins, pro-inflammatory cytokines, and placental hormones. Owing to this reaction against environmental injuries, fetal growth and endocrine system development may be impaired, leading to low or large birth weight, or prematurity. Reduced growth in early life has been related to insulin resistance, which can be silent for years and evident in predisposed adults. The incidence of type 2 diabetes mellitus and obesity associated with sedentary lifestyle patterns and inadequate dieting behaviors in children and adolescents has rapidly increased during the last decade.Recent evidences suggest that the Pro12Ala polymorphism of the peroxisome proliferator-activated receptor-? (PPAR-?) gene and the angiotensin converting enzyme (ACE) I/D gene polymorphism combined with environmental factors, such as phthalates interfering with the post receptorial action of insulin, alter insulin-sensible tissues. Therefore, IS, deriving from a complex interaction between genotype and environment, may change during life and depends on previous metabolic control, which is a sort of metabolic memory. The goal for the future is preventing the complications associated with impaired IS through the control of exogenous factors and the use of drugs selectively effective on its pathogenesis.