Fingerprinting and Groundwater Model Application to Evaluate Hydraulic Barrier Efficiency (Italy)

Remediation actions at contaminated sites are based on multiple numerical model scenarios considering different parameter distributions, source positions and contaminant transport paths. In some cases the excess of scenarios is due to uncertainties in the conceptual model as a result of the spread of contamination through heterogeneities in the physical system. Reduction of project hypotheses and conceptual model uncertainty is therefore needed. This result can be achieved by coupling hydrogeological investigations with environmental forensic techniques, better localization of the source and understanding of contamination history. In this respect, in the present study, compositional fingerprinting and groundwater flow modeling were applied to a former oil storage facility where, even though a hydraulic barrier had been built to stop the hydrocarbon plume, the presence of some hydrocarbons was still found in downgradient monitoring wells. The final aim was to evaluate the efficacy of the hydraulic barrier and identify of the source of pollution. Fingerprinting results indicated pollution with a gasoline-diesel mixture much altered by water washing and/or biodegradation. Comparison of seven groundwater samples collected in wells and monitoring wells was performed by analyzing the volatile fraction (BTEX) and the total ion chromatogram (TIC), focusing attention on: n-alkanes (m/z 85), alkylcyclohexanes (m/z 83), isoprenoids (m/z 113), C4-alkylbenzenes (m/z 134), C3-C6 alkylbenzenes and polycyclic aromatic hydrocarbons (PAHs). The most probable scenario was then identified by combining the results of fingerprinting with different contaminant paths obtained using the numerical model.     

Evaluation of epoxiconazole bioavailability in soil to the earthworm <Emphasis Type="Italic">Aporrectodea icterica</Emphasis>

In soil, the determination of total concentration using an exhaustive extraction method has little relevance to evaluate the exposure of an organism to a chemical, because of sorption processes. This study aims to propose a mild extraction method to evaluate the bioavailability of the fungicide epoxiconazole to the earthworm Aporrectodea icterica. Experiments were conducted in soils presenting various textures and organic carbon contents, spiked with formulated epoxiconazole 7 to 56 days prior to their extraction. In parallel, the epoxiconazole concentration was determined in exposed earthworms and the fungicide’s effects were evaluated by measuring weight gain, enzymatic activities and total protein contents. Among the various mild chemical solvents tested to evaluate the environmental availability of the fungicide, the 50 mM hydroxypropyl-β-cyclodextrin solution allowed to extract around 30 % of epoxiconazole. This percentage corresponded to the ratio determined in exposed A. icterica under similar soil conditions. Furthermore, this mild method was demonstrated to be sensitive to soil sorption capacities and to ageing. The mild extraction method was then applied to explore the relationship between total and (bio)available concentrations in soil and in A. icterica, over 7- or 28-day exposure time. This demonstrated the proportionality between epoxiconazole concentration in earthworm and available in soil (up to 96 %, with regression coefficient R ²?=?0.98). Sublethal effects on earthworm remained not significant.     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready–to–use EXtrelut®NT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005–0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r²? 0.99) was found in the range 0.0005–0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70–103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.     

<Emphasis Type="Italic">Aporrectodea caliginosa</Emphasis>, a relevant earthworm species for a posteriori pesticide risk assessment: current knowledge and recommendations for culture and experimental design

Ecotoxicological tests with earthworms are widely used and are mandatory for the risk assessment of pesticides prior to registration and commercial use. The current model species for standardized tests is Eisenia fetida or Eisenia andrei. However, these species are absent from agricultural soils and often less sensitive to pesticides than other earthworm species found in mineral soils. To move towards a better assessment of pesticide effects on non-target organisms, there is a need to perform a posteriori tests using relevant species. The endogeic species Aporrectodea caliginosa (Savigny, 1826) is representative of cultivated fields in temperate regions and is suggested as a relevant model test species. After providing information on its taxonomy, biology, and ecology, we reviewed current knowledge concerning its sensitivity towards pesticides. Moreover, we highlighted research gaps and promising perspectives. Finally, advice and recommendations are given for the establishment of laboratory cultures and experiments using this soil-dwelling earthworm species.     

Organochlorine pesticides and polychlorinated biphenyls in common buzzard (<Emphasis Type="Italic">Buteo buteo</Emphasis>) from Sicily (Italy)

In the present study, we investigated the concentrations and distribution of organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in intestine, liver, and muscle samples of 11 common buzzards (Buteo buteo) from Sicily used as bioindicator for monitoring pollution in environment. All samples of common buzzards were collected at the “Recovery Center of Wild Fauna” of Palermo, through the Zooprophilactic Institute. Quantitative determination of OCs and PCBs in the samples examined has been carried out using HRGC-ECD and GC-MS. The results obtained show the presence of concentrations of ∑DDT and ∑PCB in almost all samples. Regarding ∑DDT (4,4^′-DDE, 2,4^′-DDD, 4,4^′-DDD, 2,4^′-DDT, and 4,4^′-DDT), the highest concentrations were found in intestine (0.411 ± 0.050 μg/g) followed by muscle (0.130 ± 0.017 μg/g) and liver samples (0.109 ± 0.014 μg/g). As regards the ∑PCB congeners (PCB-28, PCB-52, PCB-95, PCB-99, PCB-101, PCB-110, PCB-138, PCB-146, PCB-149, PCB-151, PCB-153, PCB-170, PCB-177, PCB-180, PCB-183, and PCB-187), the highest concentrations were found in intestine (1.686 ± 0.144 μg/g) followed by liver (1.064 ± 0.162 μg/g) and muscle samples (0.797 ± 0.078 μg/g). Our data deserve particular attention not only for their significance but especially because they were recorded in Sicily, a region with a very low risk of environmental pollution due to the shortage of industries.     

The digital representation of safety systems at “Seveso” plants and its potential for improving risk management

At Seveso plants, duty holders must have a complex system for assessing and managing risks. The pillars of this system are the safety report and the safety management system, with a number of underlying documents. The strength of the system is the high standardization of these documents. Regulations, standard codes and guidelines define content, structure and formats. The weakness is the high complexity. Managers and workers perceive documents as difficult to understand and far from actual operations. Major threats for the credibility of documents (and therefore for the safety systems) come from the continuous organizational and technical changes, which in a short time can make most documents obsolete; as well as by near misses, which continuously show the holes in safety systems. A big effort is required to follow up the plant changes and the near misses. In order to help safety managers, a new software has been developed. At Seveso plants, it has been possible build an integrated digital representation, because all documents are perfectly structured. This representation may be used both for updating the relevant documents after a change and to improve documents after a near miss or an accident. In this way, safety documents are always up to date and trustworthy and the huge knowledge, which is usually hidden inside safety documents, is clearly revealed and revived. The approach is basically “knowledge based” and the intention is to provide safety managers with an easy and simple tool. IRISonLine is a software that has been developed by ISPESL to provide safety managers of “Seveso” establishments with a tool for improving the management of change and of near misses.     

Delivery and frequency distributions of combined wastewater collection system wet and dry weather loads

Combined wastewater collection systems continue to serve as a common urban conveyance method in urban areas of Europe and older urban areas of the United States. This study uses combined wastewater collection system monitoring data from the urbanizing Liguori catchment and channel in Cosenza (Italy) to illustrate event-based delivery and distribution of conveyed pollutant indices. Motivated by recent European Union (EU) discharge control legislation, this study specifically differentiates the event-based delivery of these indices between dry and wet-weather flows. Although the relatively steady to diurnal-variable delivery phenomena in dry weather flows are known, transport limiting phenomena for wet-weather hydrology and mass delivery typically are not known for the same catchment. Limiting categories of transport for a pollutant phase are generated by variables such as flow volume and duration, stream power, hydrograph parameters, and previous dry hours (PDH). Transport limitations of wet and dry weather events from the 414-ha catchment were analyzed and characterized as limited by mass indices (first-order, first flush transport) or limited by flow (zero-order transport). Results indicated significant concentration differences between mass- and flow-limited events. Higher concentrations were associated with mass-limited events. Frequency distributions of flow, total suspended solids (TSS), chemical oxygen demand (COD), and five-day biochemical oxygen demand (BOD5) were consistently exponential for wet-weather and mass-limited events. In contrast, flow, TSS, and BOD5 concentrations were distributed normally for flow-limited events. Results indicated a reasonable linear relationship between discharged TSS, COD, and BOD5 (biochemical oxygen demand) for Liguori Channel discharges into the Crati River. Wet-weather event transport was predominately mass-limited for TSS, COD, and BOD5.     

Coastal dune systems and disturbance factors: monitoring and analysis in central Italy

This study describes the conservation status of dune systems in relation to disturbance factors in the coastal stretch of the Viterbo province, Latium Region, Italy. Particular emphasis was given to the bioindication value of plant communities and their sequence. Each plant community was considered as a "habitat" in accordance with Annex I of the Directive 92/43/EU. Stress factors, such as sand dynamic and erosion, and anthropogenic pressures, such as trampling and bathing settlements, influence the sequence of habitats and weaken the system of relations that makes these coenoses to occur in extreme conditions. The choice to carry out surveys along wide transects, recording different data, allowed to explore the use of habitats as bioindicators. Comparing sites characterized by the same extension in a homogeneous area, it was possible to expand the use of canonical correspondence analysis (CCA) as a tool to correlate habitat composition and disturbance factors. The application of CCA showed a high correlation of degradation and habitat loss with coastal erosion, trampling and presence of waste. Furthermore, floristic surveys allowed the application of different biodiversity indices to quantify species richness of sampled areas. The conservation status of the sites investigated was found to be diverse, from the total disappearance of the mobile dune habitats to their complete sequence. The proposed methodology has been useful to fulfill the objective of the work and is applicable to other case studies in the Mediterranean.