Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.     

Determination of 5-ethylidene-2-norbornene in industrial emission

A method to measure the emissive concentration of 5-ethylidene-2-norbornene (ENB), a reactive compound used in industrial synthesis of terpolymers, has been developed. The starting points for the development of the presented method are European and Italian reference methods for the quantification of nonreactive volatile organic compounds in industrial emission. In this study, sampling conditions and desorption solvent have been optimized in laboratory and the method was applied in an industrial plant. The laboratory tests showed a good recovery (88–95 %). The concentrations of ENB in industrial emission obtained with the developed method were compared with an online gas chromatography–flame ionization results (R ²?>?0.97). In addition, several manual measurements were performed in parallel, and the resulting %RSD repeatability was <9 %. The developed method provides a discontinuous technique to measure reactive volatile organic compounds using easy-to-use instruments and assures a very good accuracy and precision even with high-humidity gas flows. The method could be extended to other reactive compounds of the same class.     

Vitellogenin gene expression in males of the Antarctic fish Trematomus bernacchii from Terra Nova Bay (Ross Sea): a role for environmental cadmium?

Synthesis of vitellogenin (VTG) in male fish is a widely recognized effect for estrogenic pollutants in temperate environments, while similar investigations are still lacking for Antarctic organisms. In this study, a preliminary characterization of vitellogenin gene expression was performed by RT-PCR in the key species Trematomus bernacchii sampled in different phases of reproductive cycle and food availability. Females exhibited the highest gene expression during the spawning period, but VTG mRNA was always detected also in males; a significant increase of gene expression was observed both in males and females at the end of the feeding season. These results were not fully supported by a differential exposure to phyto- or anthropogenic estrogens during the planctonic cycle; on the other side, the endocrine properties of cadmium, naturally elevated in Terra Nova Bay and increasing during algal bloom, would explain both the presence of VTG mRNA in males and the seasonal changes of gene induction. Laboratory exposures did not reveal short-term estrogenic effects of cadmium while an elevated responsiveness of T. bernacchii was observed toward a classical estrogenic receptor agonist (17beta-estradiol). Different hypotheses were considered to suggest delayed endocrine effects of cadmium, including the early interaction with other cellular detoxification systems or alterations at multiple levels of the hypothalamus-pituitary-gonad-liver axis. Although molecular mechanisms of VTG gene expression in males of T. bernacchii remain unclear, obtained results provide interesting insights on this species which should stimulate future research activities.     

Pharmaceuticals in the Environment in Italy: Causes, Occurrence, Effects and Control

- DOI: http://dx.doi.org/10.1065/espr2006.01.004 Background, Aim and Scope Environmental contamination by pharmaceuticals is an emerging issue. Until recently, information on medicinal substances released into the environment was scant, but several studies have now been published. Data are, however, usually scattered and a systematic approach to this subject is generally lacking. Moreover, because of differences in the prevalence of diseases, treatment habits and options, or simply for market reasons, the pollution profile can differ significantly in different countries. The aim of this work is to review the papers dealing with environmental contamination by pharmaceuticals in Italy, with the aim of providing a comprehensive view on a national scale. Methods Papers related to environmental contamination by pharmaceuticals in Italy were reviewed, in order to offer a comprehensive view of this subject. Topics included analysis, occurrence, monitoring, modelling, treatment, control of the emissions, and ecotoxicological effects of pharmaceuticals in the environment. Results and Conclusion The literature suggests that pharmaceuticals are widespread contaminants, entering the environment from a myriad of scattered points. Patients, in case of drugs for human use, or animals for veterinary drugs, are the main sources of contamination. Pharmaceuticals can be ranked according to environmental loads, predicted by multiplying sales figures by the rate of metabolism in man or animals. Priority pharmaceuticals, i.e. the molecules of concern for the environment, can be measured in waste and surface water by liquid chromatography-tandem mass spectrometry, and the loads detected are generally comparable to the predicted ones. Pharmaceuticals are designed to stimulate a response in humans and animals at low doses, with a very specific target, so the implications for human health and the environment need to be assessed. In vitro and in vivo studies suggest that pharmaceutical principles, taken singularly or in combinations, and concentrations close to those detected in the environment, may have ecotoxicological effects. The sewage system is an important point in the control of contamination, but sewage treatment plants are not able efficiently to abate a substantial part of water-borne pharmaceuticals. Several variables play a role, however, in the processes of waste water treatment, and could be specifically adjusted to improve the efficiency of drug abatement, mitigating the potential environmental hazards. Recommendation and Perspective Pharmaceuticals in the environment are becoming a subject of global concern, with potential environmental consequences. Further knowledge of the causes, occurrence and effects of drugs as environmental pollutants is necessary for a better understanding of this ecological issue, as well as to improve abatement strategies, and to mitigate subtle environmental consequences.     

Evaluating mortality rates with a novel integrated framework for nonmonogamous species

The conservation of wildlife requires management based on quantitative evidence, and especially for large carnivores, unraveling cause‐specific mortalities and understanding their impact on population dynamics is crucial. Acquiring this knowledge is challenging because it is difficult to obtain robust long‐term data sets on endangered populations and, usually, data are collected through diverse sampling strategies. Integrated population models (IPMs) offer a way to integrate data generated through different processes. However, IPMs are female‐based models that cannot account for mate availability, and this feature limits their applicability to monogamous species only. We extended classical IPMs to a two‐sex framework that allows investigation of population dynamics and quantification of cause‐specific mortality rates in nonmonogamous species. We illustrated our approach by simultaneously modeling different types of data from a reintroduced, unhunted brown bear (Ursus arctos) population living in an area with a dense human population. In a population mainly driven by adult survival, we estimated that on average 11% of cubs and 61% of adults died from human‐related causes. Although the population is currently not at risk, adult survival and thus population dynamics are driven by anthropogenic mortality. Given the recent increase of human‐bear conflicts in the area, removal of individuals for management purposes and through poaching may increase, reversing the positive population growth rate. Our approach can be generalized to other species affected by cause‐specific mortality and will be useful to inform conservation decisions for other nonmonogamous species, such as most large carnivores, for which data are scarce and diverse and thus data integration is highly desirable.     

Simulating pesticide leaching and runoff in rice paddies with the RICEWQ-VADOFT model

There is a current need to simulate leaching and runoff of pesticide from rice (Oryza sativa L.) paddies for assessing environmental impacts on a valuable agricultural system. The objective of this study was to develop a model for determining predicted environmental concentration (PEC) in soil, runoff, and ground water through the linkage of two models, rice water quality model (RICEWQ) and vadose zone transport model (VADOFT), to simulate pesticide fate and transport within a rice paddy and underlying soil profile. Model performance was evaluated with a field data set obtained from a 2-yr field experiment in 1997 and 1998 in northern Italy. The predictions of amount of pesticide running off from the paddy field and accumulating in the paddy sediment were in agreement with measured values. Leaching into the vadose zone accounted for approximately 19% of the applied dose, but only a small amount of chemical (<0.1%) was predicted to reach ground water at a 5-m depth due to sorption and transformation in the soil. The permeability of the soil and the water management practices in the paddy field were shown to have a strong influence on pesticide fate. These factors need to be well characterized in the field if model predictions are to be successful. The combined model developed in this work is an effective tool for exposure assessments for soil, surface water, and ground water, in the particular conditions of rice cultivation.     

Predicting and measuring environmental concentration of pesticides in air after soil application

Pesticides can volatilize into the atmosphere, which affects the air quality. The ability to predict pesticide volatilization is an essential tool for human risk and environmental assessment. Even though there are several mathematical models to assess and predict the fate of pesticides in different compartments of the environment, there is no reliable model to predict volatilization. The objectives of this study were to evaluate pesticide volatilization under agricultural conditions using malathion [ O,O-dimethyl-S-(1,2-dicarbethoxyethyl)-dithiophosphate], ethoprophos (O-ethyl S,S-dipropylphosphorodithioate), and procymidone [N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide] as test compounds and to evaluate the ability of the Pesticide Leaching Model (PELMO) to calculate the predicted environmental concentrations of pesticides in air under field conditions. The volatilization rate of procymidone, malathion, and ethoprophos was determined in a field study during two different periods (December 1998 and September 1999) using the Theoretical Profile Shape (TPS) method. The experiments were performed on bare silty soil in the Bologna province, Italy. Residues in the air were continuously monitored for 2 to 3 wk after the pesticide applications. The amount of pesticide volatilized was 16, 5, and 11% in December 1998 and 41, 23, and 19% in September 1999 for procymidone, malathion, and ethoprophos, respectively. In both these experiments, the PELMO simulations of the concentration of ethoprophos and procymidone were in good agreement with the measured data (factor +/- 1.1 on average). The volatilization of malathion was underestimated by a factor of 30 on average. These results suggest that volatilization described by PELMO may be reliable for volatile substances, but PELMO may underpredict volatilization for less-volatile substances.     

Pesticide removal from waste spray-tank water by organoclay adsorption after field application to vineyards

Purpose

The main objective of this work was to develop and test a pilot scheme for decontaminating pesticide-containing water derived from pesticide mixtures used to protect vineyards, in which the scheme comprises adsorption by an organoclay and includes a system where an enhanced or rapid microbial degradation of the adsorbed residues can occur.

Methods

In laboratory experiments, the Freundlich adsorption coefficients of formulations of two fungicides, penconazole and cyazofamid, onto the organoclay Cloisite 20 A were measured in order to predict the efficiency of this organoclay in removing these fungicides from the waste spray-tank water. Subsequently, the adsorption tests were repeated in the pilot system in order to test the practical operation of the depuration scheme.

Results

The adsorption tests with the pilot system show 96% removal of both fungicides over a few hours, similar to the efficiency of removal predicted from the laboratory adsorption tests. The formulation type may influence the efficiency of clay recovered after adsorption. Regarding the waste disposal, for instance, the organoclay composted after the treatment, cyazofamid showed significant dissipation after 90?days, whereas the dissipation of penconazole was negligible.

Conclusion

The depuration scheme developed showed to be efficient for decontaminating pesticide-containing water derived from vineyards, but additional treatments for the adsorbed residues still appear to be necessary for persistent pesticides. However, future decontamination research should be attempted for water contaminated with pesticides containing antifoaming agents in their formulations, in which case the present pilot system could not be applied.