Silvana Galassi

Selection of priority properties to assess environmental hazard of pesticides

Abstract We assess the environmental hazard of 50 pesticides used in Italy by means of Hasse diagrams, a method based on graph theory. The criteria we use for ranking are persistence, and the physical-chemical properties, vapour pressure and water solubility, and yearly usage. When only the physical-chemical properties plus persistence are used to assess environmental hazard of pesticides in soils, eleven out of the 50 compounds studied here, methylbromide, bentazone, dalapon, diquat, linuron, mancozeb, metham-Na, TCA, metolachlor, paraquat, and simazine are considered potentially hazardous for the combination of long persistence in soil, high water solubility and low vapour pressure. Alachlor, atrazine, chloridazon, terbuthylazine and ziram are also a problem of concern because of their high loadings. To test whether the theoretical ranking is realistic, the list of identified compounds was compared with the results of monitoring studies carried out in the River Po. The assumption for this comparison is that, if the ranking method is correct, the probability of finding chemicals identified as hazardous should be higher than the probability of finding less hazardous chemicals. Chemicals ranked lower have less probability of being found both because of lower usage and because they are less persistent and/or less leachable. Results are quite encouraging since seven pesticides identified by our ranking method as most hazardous, alachlor, atrazine, bentazone, linuron, metolachlor, simazinc and terbuthylazine of the 8 analyzed for (previous plus TCA) were found, a success ratio of 88%. Results for all the other chemicals are presented in the paper. The second purpose of this study was the identification of the most important criteria to assess the chemicals; this assessment was performed using a matrix W. We concluded that the elimination of the criterion “usage” affects ranking more than the elimination of water solubility. However, none of the criteria, water solubility, vapour pressure, persistence and yearly usage can be eliminated, too much information would be lost if they were omitted. This conclusion is consistent with our decision to use only few criteria to rank the chemicals, criteria that are deemed to be independent of each other.

Quality assessment of bed sediments of the Po River (Italy).

Comprehensive and contemporary evaluations of physical, chemical and toxicological endpoints have been performed on bed sediments of the Po River, the major Italian watercourse. Two extensive sampling campaigns were conducted in summer and winter low-flow conditions. Composite sediment samples were collected from ten reaches of the main river: the first was located in the upper region (ambient control), and the others downstream of the confluences of nine principal tributaries. The two sampling programs were paralleled by contemporary investigations on the macroinvertebrate community. The particle-size composition along the Po River showed a relatively uniform distribution of fine sand, a progressive downstream decrease of coarse sands and a corresponding increase of fine materials. The levels of polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), extractable organo halides (EOX), Cd, Cr, Cu, Hg, Ni, Pb and Zn were determined in sediment fine particles (< 63 microm), and showed marked changes across the ten river reaches. Their longitudinal trends, as those of organic carbon and total nitrogen, were very similar and largely independent of the survey season. Sediment quality benchmarks were used to evaluate sediment chemistry, and, although the overall level of contamination was from moderate to low, the reaches located downstream of the tributaries Dora Riparia, Dora Baltea, Lambro and Oglio were considered to be at risk. Sediments were tested for toxicity on Oncorhynchus mykiss, Ceriodaphnia dubia, Raphidocelis subcapitata and Vibrio fischeri. The toxicity tests were conducted both with sediment extracts and whole samples. Sediment extracts showed toxic potentials that were consistent with the spatial distribution of contaminants. Whole-sediment toxicity showed moderate/low effects which also included false positives and negatives. Alterations of the macroinvertebrate community were found for many kilometers downstream of Dora Riparia, and with a seasonal dependence, also in other reaches of the Italian river. Principal component analysis (PCA) was used to describe the longitudinal and temporal changes of the Po River, and allowed the selection of the most useful and discriminating indicators.

DDT contamination in Lake Maggiore (N. Italy) and effects on zebra mussel spawning.

Zebra mussel (Dreissena polymorpha) is commonly used as contaminant bioindicator in Europe and North America. We used the zebra mussel to follow DDT pollution trends from 1996 to 1997 in Pallanza bay, Lake Maggiore, near the inlet of the River Toce, after a DDT-manufacturing plant discharging residues into a tributary of the River Toce had closed down. DDT contamination fell off sharply outside the bay, but tissue concentrations of the parent compound and residues remained high in molluscs sampled within the bay a year later. Molluscs collected in Pallanza bay in June 1997 released gametes earlier than those sampled at a nearby reference station. Histological studies showed that a significant percentage of these specimens showed marked oocyte degeneration suggesting that DDTs have endocrine-disrupting effects in this species.

Assessment of river Po sediment quality by micropollutant analysis.

Trace metals, PCB congeners and DDT homologues were determined in composite sediment samples collected from 10 representative sites along the river Po in two separate seasons. The aim was to identify the most anthropogenically impacted areas for future monitoring programmes and to aid development of Italian sediment quality criteria. The surface samples were collected during low flow conditions. Trace metal concentrations were assayed by electrothermal (Cd, Co, Cr, Cu, Ni, Pb), flame (Fe, Mn, Zn) or hydride generation (As) atomic absorption spectrometry after microwave assisted acid digestion. Hg was determined on solid samples by automated analyser. Organic microcontaminants were determined by gas-chromatography with 63Ni electron capture detector after Soxhlet extraction. Concentrations of trace metals, total PCB and DDT homologues showed two distinct peaks at the sites immediately downstream of Turin and Milan, respectively, and in each case decreased progressively further downstream. Principal component analysis identified three major factors (from a multi-dimensional space of 35 variables) which explained 85-90% of the total observed variance. The first and second factors corresponded to anthropogenic inputs and geological factors on sediment quality; the third included seasonal processes of minor importance. Sediment quality assessment identified Cd, Cu, Hg, Pb, Zn and organic microcontaminants as posing the most serious threats to river sediment quality. A reference site within the Po basin provided useful background values. Moderate pollution by organochlorine compounds was ascribed both to local sources and to atmospheric deposition.

Toxicological and chemical characterization of organic micropollutants in river po waters (Italy)

River Po waters were collected at the end of the drainage basin, extracted by means of XAD-2 resins and tested for toxicity on aquatic organisms (Daphnia magna and Selenastrum capricornutum) and for mutagenicity with a modified Ames test. The extracts were analyzed by HRGC/FID and selective detectors for the determination of the most common classes of toxic compounds. The relationships between toxicological responses and analytical results are discussed.

Toxicity of 4-nonylphenol in spiked sediment to three populations of Chironomus riparius.

Nonylphenols (NPs) are the primary stable metabolites of alkylphenol polyethoxylates (APEs), a family of compounds widely used in industry and in some domestic products. As NPs accumulate in sediments in aquatic environments, the risk to benthic organisms needs to be assessed. In this study 4NP-spiked sediments were tested on larvae of the dipteran Chironomus riparius. First instar larvae obtained from populations at three different sources were used. To spike the sediments, an equilibration procedure between water and sediment was adopted to avoid the use of solvents. Lower 10-d LC50 values were determined for two populations of C. riparius from clean environments (315-465 and 315-350 microg g(-1) d.w., respectively) than those of a strain deriving from a population collected in a polluted river (600-680 microg g(-1) d.w.). Larval growth always decreased with increasing 4NP concentration but without any defined trend. The results of this study suggest that tolerance to the toxicant can be developed in populations of polluted environments and that testing procedures should be standardised.

Factors Affecting the use of Dreissena polymorpha as a Bioindicator: the PCB Pollution in Lake Como (N. Italy)

The aim of this study was to assess the PCB pollutionof the South-Western branch of Lake Como by using thezebra mussel (Dreissena polymorpha) as abioindicator since its recent reintroduction. Someenvironmental and physiological variables influencingaccumulation processes of organochlorine compounds inDreissena were investigated because climaticfactors may affect life cycle, reproductive stage andage. PCB levels were highest in the soft tissues ofDreissena close to the industrialized area ofComo (2298 ng g-1 of lipids) and slowly decrease goingnorth, reaching approximately half this value at theclosing section of the lake branch. Nonetheless, thePCB concentrations are well below the dangerous levelsfor the aquatic environment.

Approaches to modeling toxic responses of aquatic organisms to aromatic hydrocarbons

Acute toxic effects on Salmo gairdneri, Poecilia reticulata, Daphnia magna, and the growth inhibition of Selenastrum capricornutum were measured for eight aromatic hydrocarbons. Toxicity measurements were carried out following the OECD standard guidelines modified as appropriate in order to prevent hydrocarbon loss by volatilization; the concentrations of the substrates in the test solutions were periodically measured by HPLC. The toxic responses were analyzed in terms of the n-octanol/water partition coefficients, by means of linear regression analysis, and in terms of five molecular properties simultaneously, by means of the partial least squares analysis in latent variables (PLS). The univariate and multivariate quantitative structure-activity relationship models obtained by the two approaches are compared and discussed.

The fate of triazine pesticides in River Po water

A group of triazine herbicides has been monitored in river Po water over a period of three years. The N-deethylated metabolite of atrazine was also found. Laboratory tests of biodcgradation of triazine performed with River Po water as cultural medium did not show any significant triazine degradation, leading to the conclusion that triazine metabolites derive from de.~-adation in soil. The chemical reactivity of triazines toward oxidants was also tested in laboratory with lead(IV) acetate, cerium(IV) ammonium nitrate and ozone. A chemical degradation pathway for triazines is suggested.

The distribution of PCB's and chlorinated pesticides in two connected Himalayan lakes

PCBs and organochlorine pesticides were determined in water, sediment and Zooplankton of two Himalayan lakes, located at different altitudes and connected to each other in such a way that Superior Lake acts as a sedimentation basin for Inferior Lake. Surficial sediments of both lakes show PCB contamination comparable to lakes of industrialised areas. Biota appear to be the main machanism responsible for micropollutant burial in the sediments of Inferior Lake, whereas inorganic particles are more relevant in Superior Lake. Physical and chemical properties of individual chemicals, particularly Henry’s law constant and Kow values, seem to regulate distribution in different environmental compartments.