Innovative aspects of environmental chemistry and technology regarding air,water, and soil pollution

Environmental Science and Pollution Research -     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

Assessment of Aquifer Vulnerability in an Agricultural Area in Spain Using the DRASTIC Model

The assessment of aquifer vulnerability is a very important task, especially in agricultural areas because the quality and availability of groundwater affects both the sustainability of agriculture and the quality of life. In this study, an integrated approach is considered, with the use of the generic and agricultural DRASTIC models as well as a geographic information system (GIS), to assess groundwater vulnerability in the agricultural area of Barrax, in the province of Albacete, in Spain. Seven parameters—depth to water, net recharge, aquifer media, soil media, topography, impact of vadose zone media, and hydraulic conductivity of the aquifer (DRASTIC)—have been considered as weighted layers to enable an accurate groundwater risk mapping. The results of the generic DRASTIC model indicated very low vulnerability to contamination for Barrax groundwater due to limited urban and industrial development in the wider area. However, agricultural activities impose pressure to groundwater resources and the results of the agricultural DRASTIC model show that 6.86% of the study area is characterized by very high, 2.29% by high, 47.28% by medium, 38.28% by low, and the remaining 5.29% by no vulnerability to groundwater contamination. The distribution of nitrate concentration in groundwater in the area under study is quite well correlated with the agricultural DRASTIC vulnerability index. Sensitivity analysis was also performed to acknowledge statistical uncertainty in the estimation of each parameter used, to assess its impact, and thus to identify the most critical parameters that require further investigation. Depth to water and impact of vadose zone are the parameters that had the most noticeable impact on the generic DRASTIC vulnerability index followed by the soil media and topography. In contrast, the agricultural DRASTIC method is more sensitive to the removal of the depth to water parameter followed by the topography and the soil media parameters.     

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

Modelling biodegradation of hydrocarbons in aquifers: when is the use of the instantaneous reaction approximation justified?

In-situ bio-remediation is a viable cleanup alternative for aquifers contaminated by hydrocarbons such as BTEX. Transport models of varying complexity and capabilities are used to quantify their degradation. A model that has gained wide acceptance in applications is BIOPLUME II, which assumes that oxygen-limited biodegradation takes place as an instantaneous reaction. In this work we have employed theoretical analysis, using non-dimensional variables, and numerical modelling to establish a quantitative criterion demarcating the range of validity of the instantaneous reaction approximation against biodegradation kinetics. Oxygen was the limiting species and sorption was ignored. This criterion relates (o), the Dahmk?hler number at oxygen depletion, to O(o)*, the ratio of initial to input oxygen concentration, (o) > or = 0.7(O(o)*)(2) + 0.1O(o)* + 1.8. The derived (o) reflects the intrinsic characteristics of the physical transport and of the biochemical reaction, including the effect of biomass density. Relative availability of oxygen and hydrocarbons exerts a small influence on results. Theory, verified and refined via numerical simulations, showed that significant deviations of instantaneous reactions from kinetics are to be expected in the space-time region s相似文献   

Levels, sources and spatiotemporal variation of nutrients and micropollutants in small streams of a Mediterranean River basin

In this study, nutrients, trace metals and priority pesticide compounds were investigated for the first time in water and sediment samples in streams of the Evrotas River basin (S.E. Greece) from 2006 to 2008. The most important sources of contamination were from the entry of pesticides and nutrients into surface waters and sediments as a result of the intensive agricultural activity as well as from the uncontrolled disposal of olive mill and citrus processing wastewaters. Aquatic risk assessment revealed that all insecticides detected showed high risk, suggesting adverse effects on the stream biota. Among the metals analyzed, Cr, Ni and Ba presented the highest concentrations in sediments, however, due to natural geological processes. Multivariate statistical techniques applied for data compression, exploration and interpretation proved to be useful tools for identifying the most critical pollutants affecting the surface water quality. The findings of this study suggest that the inclusion of streams with small catchment areas into WFD monitoring and assessment programs is essential, especially those of the Mediterranean region.     

Experimental evaluation of the energy balance in Octopus vulgaris, fed ad libitum on a high-lipid diet

A complete energy balance equation was estimated for the common octopus Octopus vulgaris at a constant temperature of 20°C, fed ad libitum on anchovy fillet (Engraulis encrasicolus). Energy used for growth and respiration or lost with faeces and excreted ammonia was estimated, along with total energy consumption through food, for six specimens of O. vulgaris (with masses between 114 and 662 g). The energy balance equation was estimated for the specimens at 10-day intervals. During each 10-day interval, food consumed, body mass increase and quantity of faeces voided were measured. The calorific values of octopus flesh, anchovy flesh and faeces were measured by bomb calorimetry. Oxygen consumption and ammonia excretion rates were monitored for each specimen during three 24-h experiments and daily oxygen consumption and ammonia excretion were estimated. It was found that 58% of the energy consumed was used for respiration. The amount of energy invested in somatic and gonadal growth represented 26% of the total energy budget. The energy discarded through faeces was 13% of consumed energy. The estimated assimilation efficiency (AE) values of O. vulgaris feeding on anchovy (80.9–90.7%) were lower than the AE values estimated for other cephalopod species with different diets of lower lipid content such as crabs or mussels. Specific growth rates (SGR) ranged 0.43–0.95 and were similar to those reported for other high-lipid diets (bogue, sardine) and lower than SGR values found for low-lipid, high-protein diets (squid, crab, natural diet). Ammonia excretion peak (6 h after feeding) followed the one of oxygen consumption (1 h after feeding). The values of atomic oxygen-to-nitrogen (O:N) ratio indicated a protein-dominated metabolism for O. vulgaris.     

Rapid whole exome sequencing in pregnancies to identify the underlying genetic cause in fetuses with congenital anomalies detected by ultrasound imaging

Objective

The purpose of this study was to explore the diagnostic yield and clinical utility of trio-based rapid whole exome sequencing (rWES) in pregnancies of fetuses with a wide range of congenital anomalies detected by ultrasound imaging.

Methods

In this observational study, we analyzed the first 54 cases referred to our laboratory for prenatal rWES to support clinical decision making, after the sonographic detection of fetal congenital anomalies. The most common identified congenital anomalies were skeletal dysplasia (n = 20), multiple major fetal congenital anomalies (n = 17) and intracerebral structural anomalies (n = 7).

Results

A conclusive diagnosis was identified in 18 of the 54 cases (33%). Pathogenic variants were detected most often in fetuses with skeletal dysplasia (n = 11) followed by fetuses with multiple major fetal congenital anomalies (n = 4) and intracerebral structural anomalies (n = 3). A survey, completed by the physicians for 37 of 54 cases, indicated that the rWES results impacted clinical decision making in 68% of cases.

Conclusions

These results suggest that rWES improves prenatal diagnosis of fetuses with congenital anomalies, and has an important impact on prenatal and peripartum parental and clinical decision making.     

Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices

BACKGROUND, AIM AND SCOPE: Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). EDCs comprise many classes of organic compounds. The development or optimization of analytical protocols for the simultaneous determination of EDCs in environmental samples is an analytical challenge because these compounds exhibit different physicochemical characteristics, they occur in the aquatic environment in relatively low concentrations and, furthermore, environmental samples are considered as complex matrices. The aim of this study is the development of analytical methods for the simultaneous determination of phenolic and steroid EDCs in aqueous and solid samples. The target compounds are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, the estrogens (estriol, estrone, 17beta-estradiol, 17alpha-estradiol) and the synthetic steroids (mestranol and 17alpha-ethynylestradiol). MATERIALS AND METHODS: Solid phase extraction employing Oasis HLB cartridges and different elution solvents was used for the recovery studies of the target compounds from various types of water samples (ultrapure water, artificial seawater, river water and seawater). Ultrasonic assisted extraction was applied for the recovery of the target EDCs from the solid samples. The recoveries were assessed using various solvents for the extraction and the elution of EDCs from different SPE cartridges used for clean up. Gas chromatography-mass spectrometry after derivatization with N,O-bis(trimethylsilyl)-trifluoroacetamide was employed for the determination of these compounds. RESULTS AND DISCUSSION: The recovery rates of three elution solvents (methanol, acetone and ethylacetate) for the extraction of target EDCs from artificial seawater were assessed after preconcentration on SPE cartridges. Acetone showed better recoveries and was further tested for its extraction efficiency in different water types (river water, seawater). Ultrasonic assisted extraction was used for the recovery of target EDCs from solid matrices. Acetone, methanol, mixture of acetone-methanol (1:1) and ethylacetate were used as extraction solvents. Ethylacetate and the mixture of acetone-methanol (1:1) exhibited better extraction efficiencies. An additional clean up step was necessary for sediment samples. Different SPE cartridges were employed for clean up of the extracts (Oasis HLB, C18, Florisil, silica, combination of silica and alumina). Florisil cartridges were finally used. The proposed methods were further validated on the determination of target EDCs in field collected samples (river water, seawater, wastewater, total suspended solids and sediments) from the major area of Thessaloniki, Greece. CONCLUSIONS: Efficient and accurate integrated methods for the simultaneous determination of alkylphenols (nonylphenol, octylphenol), their ethoxylate oligomers (mono- and di-ethoxylate of nonylphenol and octylphenol), bisphenol A and steroids (estriol, estrone, 17beta-estradiol, 17alpha-estradiol, mestranol and 17alpha-ethynylestradiol) in aqueous and solid samples were developed. The proposed methods were applied for the determination of the target compounds in representative environmental samples in the area of Thessaloniki, Northern Greece. RECOMMENDATIONS AND PERSPECTIVES: This study confirms the occurrence of selected EDCs in inland and marine waters in the area of Thessaloniki, Northern Greece. Since there is no previous data on the occurrence of the target EDCs in the major area, an extended survey is in progress to evaluate the occurrence and fate of these compounds.