Antonio Finizio

Water quality objectives for mixtures of toxic chemicals: problems and perspectives

The need to develop water quality objectives not only for single substances but also for mixtures of chemicals seems evident. For that purpose, the conceptual basis could be the use of the two existing biometric models: concentration addition (CA) and independent action (IA), which is also called response addition. Both may allow calculation of the toxicity of mixtures of chemicals with similar modes of action (CA) or dissimilar modes of action (IA), respectively. The joint research project Prediction and Assessment of the Aquatic Toxicity of Mixtures of Chemicals (PREDICT) within the framework of the IVth Environment and Climate Programme of the European Commission, provided the opportunity to address (a) chemometric and QSAR criteria to classify substances as supposedly similarly or dissimilarly acting; (b) the predictive values of both models for the toxicity of mixtures at low, statistically nonsignificant effect concentrations of the individual components; and (c) the predictability of mixture toxicity at higher levels of biological complexity. In this article, the general outline, methodological approach, and some preliminary findings of PREDICT are presented. A procedure for classifying chemicals in relation to their structural and toxicological similarities has been developed. The predictive capabilities of CA and IA models have been demonstrated for single species and, to some extent, for multispecies testing. The role of very low effect concentrations in multiple mixtures has been evaluated. Problems and perspectives concerning the development of water quality objectives for mixtures are discussed.

Environmental risk assessment for pesticides: A tool for decision making

Abstract Pesticides are widely used to protect crops and to prevent disease. However, they can also be the cause of environmental pollution. Today, ecological policy and management decision makers in many countries (i.e. EU) require sound scientific information on the environmental risk associated with pesticides in order to base and justify their decisions. Consequently, there is a need to develop predictive tools to evaluate all potential risks of environmental damage that might be caused by the use of plant protection products. This paper analyses and discusses the risk assessment approach applied in the field of pesticides. The link between environmental policy, risk assessment and risk management will also be highlighted.

QSAR approach for the selection of congeneric compounds with a similar toxicological mode of action

The selection of compounds with a similar toxicological mode of action is a key problem in the study of chemical mixtures. In this paper, an approach for the selection of chemicals with similar mode of action, based on the analysis of structural similarities by means of QSAR and chemometric methods, is described. As a first step, a complete representation of chemical structures for examined chemicals (phenylureas and triazines) by different sets of molecular descriptors allows a preliminary exploration of similarity using multi-dimensional scaling (MDS). The use of genetic algorithm (GA) to select the most relevant molecular descriptors in modeling toxicity data makes it possible to develop predictive toxicity models. The final step is a similarity analysis, based again on MDS, using selected molecular descriptors, really relevant in describing the toxicological effect.

Risk Assessment for Honeybees from Pesticide-Exposed Pollen

A method for assessing the risk for honeybees from pesticide exposure via pollen is proposed. Four pesticides, selected as markers, were monitored in pollen samples collected in two sampling areas, one located in an intensive agricultural area and the other far from direct pesticide impact. Analytical results were consistent with use patterns of the chemicals and their physico-chemical and persistence properties. For a preliminary estimate of bee exposure via pollen, both by ingestion and by contact, an exposure index was developed, based on physico-chemical properties, persistence and application rates. On the basis of the exposure estimates and acute toxicological data (ingestion and contact LD50), Toxicity Exposure Ratios (TERs) were calculated as indicators of the risk for honeybees due to this particular exposure route. TER values were compared to Hazard Quotient (HQ), calculated as the ratio between application rate and the LC50 value, according to European guidelines, showing a satisfactory agreement. The advantage of the above described procedures is that the environmental fate of the chemicals, and not only application rates, are taken into account. This approach may represent a preliminary tool for a comparative screening of the risk for pollinator insects due to this particular exposure route.

First evidences of the occurrence of polycyclic synthetic musk fragrances in surface water systems in Italy: Spatial and temporal trends in the Molgora River (Lombardia Region, Northern Italy)

The polycyclic synthetic musks (PCMs) such as galaxolide (HHCB), tonalide (AHTN) and celestolide (ABDI) are important ingredients in fragrances for consumer products because of their typical musky scent. In EU, PCMs are classified as HPVC (High Production Volume Chemicals). Furthermore, it has been recognized that these substances are only partially degraded in domestic sewers. For both reasons these chemicals are considered ubiquitous contaminants of aquatic systems. Monitoring data are available for the Northern region of the EU, but it is not known whether they are also representative for the Southern EU countries. The lack of data upon the environmental exposure in Southern EU can be significant, since use patterns and volumes differ from country to country. This is particularly true for Italy that has the largest detergent consumption per capita in EU. Due to this, the objective of the present study was to investigate the occurrence of selected PCMs in the Molgora River (Lombardia region, Italy). To our knowledge it represents the first overview of PCM occurrence in the Italian water bodies. Water samples were collected seasonally in seven sampling stations located before and after the 3 sewage treatment plants present along the river, which serve about 300,000 inhabitants. The spatial and temporal profiles of contamination are described. A comparison of the results with existing monitoring data of other European regions indicated a significant higher level of PCM pollution of the Molgora River and the need to extend the monitoring campaigns to other Italian water bodies, in order to achieve a better knowledge of the levels of PCM contamination in this country.

Environmentally relevant concentrations of galaxolide (HHCB) and tonalide (AHTN) induced oxidative and genetic damage in Dreissena polymorpha

Synthetic musk compounds (SMCs) are extensively used as fragrances in several personal care products and have been recognized as emerging aquatic pollutants. Among SMCs, galaxolide (HHCB) and tonalide (AHTN) are extensively used and have been measured in aquatic ecosystems worldwide. However, their potential risk to organisms remains largely unknown. The aim of this study was to investigate whether 21-day exposures to HHCB and AHTN concentrations frequently measured in aquatic ecosystems can induce oxidative and genetic damage in Dreissena polymorpha. The lipid peroxidation (LPO) and protein carbonyl content (PCC) were measured as oxidative stress indexes, while the DNA precipitation assay and the micronucleus test (MN test) were applied to investigate genetic injuries. HHCB induced significant increases in LPO and PCC levels, while AHTN enhanced only protein carbonylation. Moreover, significant increases in DNA strand breaks were caused by exposure to the highest concentrations of HHCB and AHTN tested in the present study, but no fixed genetic damage was observed.

Estimating ecotoxicological effects of pesticide drift on nontarget arthropods in field hedgerows.

When hedgerows grow in orchards where pesticides are applied, they can play a double role: Providing a barrier for chemical spray drift and as a refuge for beneficial arthropods such as pollinators and predators. Effectiveness of hedgerows as barriers to drift depends mainly on canopy density (that can be estimated through optical porosity) and wind speed. When optical porosity is low, the hedgerow can intercept a significant amount of spray drift and act as an effective barrier, but the intercepted pesticide can negatively affect the beneficial arthropods living there. A drift model was used to simulate drift in a hedgerow- vineyard system, and a deposition distribution model was used to calculate the pesticide spatial pattern distribution on a hedgerow with different optical porosity and wind speed conditions. The possible ecotoxicological effects were estimated for 28 active ingredients with different median lethal rates for two nontarget arthropods, Aphidius rhopalosiphi and Typhlodromus pyri. A spatialized risk assessment for a hedgerow is suggested to improve procedures based on application rate, standard drift, and vegetation distribution values, as in the hazard quotient approach. An alternative method for calculation of the exposure is also proposed, with a step-by-step example of a toxicity/exposure ratio calculation. The results highlighted the importance of the spatial pattern of drift and proved that a hedgerow can be an effective barrier against spray drift. Analysis of the toxicity/exposure ratio values showed that a hedgerow can continue its shelter and feeding function for nontarget arthropods when low-toxicity pesticides are used, there is no significant wind interference, or both.

Experimental and predicted acute toxicity of antibacterial compounds and their mixtures using the luminescent bacterium Vibrio fischeri

This article investigates the bioluminescence inhibition effects of the antimicrobials triclocarban, triclosan and its metabolite methyl triclosan, using the marine bacterium Vibrio fischeri as the test organism (Microtox©). The concentration response analysis was performed for the three individual substances and for a mixture in which the three compounds were mixed in a ratio of the IC50 of the individual components (equitoxic ratio). Toxicity values (the median inhibitory concentration value, in mg L(-1)) in the decreasing order of sensitivity were triclosan (0.73)>triclocarban (0.91)>methyl-triclosan (1.76). The comparison of the experimental data with those obtained by using Quantitative Structure-Activity Relationship (QSAR) equations indicated that triclosan and triclocarban act as polar narcotic compounds towards V. fischeri, whereas methyl-triclosan acts as a narcotic (baseline toxicity). The toxicity of the mixture was measured experimentally and predicted by two models (CA: concentration addition; IA: independent action). The results showed that the observed mixture toxicity (IC50=0.23 mg L(-1)) had no significant differences from those predicted by both CA and IA models.

Effects of river pollution on the colonisation of artificial substrates by macrozoobenthos

The impact of pesticides on macrobenthos communities was studied on two aquatic environments in Northern Italy; River Meolo, a site exposed to agricultural pollution, and River Upper Livenza a low pollution reference site. Colonisation of artificial substrates was compared throughout the productive season. The relevance of multiple environmental stressors other than pesticides (e.g. oxygen depletion) was also assessed. Biochemical indicators (enzyme and metabolite biomarkers) were measured on selected organisms. Biomarker results (acetylcholinesterase, glutathione S-transferase, and napthylacetate esterase), as well as community structure patterns, revealed a significant difference between the two rivers. Cause-effect relationships between results and multiple stress factors were discussed.

Assessing the environmental risks associated with contaminated sites: Definition of an Ecotoxicological Classification index for landfill areas (ECRIS)

Assessing ecological risk in quantitative terms is a site-specific complex procedure requiring evaluation of all possible pathways taken by the chemicals from the contamination source to the targets to be protected. Unfortunately, too many cases lack of physico-chemical and ecotoxicological data makes impossible to quantify the ecological risk. We present the Ecotoxicological Classification Risk Index for Soil (ECRIS), a new classification system specific for soil risk assessment, which gives a comparative indication of the risk linked to environmental contamination by any chemical. The tool we propose is based on the integration of a data set characterizing the ecotoxicological and exposure profile of chemicals. ECRIS is a simple approach specifically set up for the landfill scenario. This index draws on the huge amount of data from our many years of leachate analysis. ECRIS is useful for a first screening of probably contaminated soil. A case study based on some Italian landfills is proposed.