Part II: temporal and spatial distribution of multiclass pesticide residues in lake sediments of northern Greece: application of an optimized MAE-LC-MS/MS pretreatment and analytical method

The development and application of an analytical methodology for the pretreatment and determination of 253 multiclass pesticides, in lake sediment samples, using liquid chromatography coupled with mass spectrometry (LC-MS/MS) are described in this work. Sediments of lakes Volvi, Doirani, and Kerkini, located in northern Greece, were collected in two-time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methodology. Microwave-assisted extraction (MAE) was applied to extract the pesticide residues from lake sediment samples. Analytical results were stored, categorized, and visualized using geographical information systems, in order to assess and observe spatial and temporal variations of the pollution. Main pesticides that were detected included the following: amitrole, tebuconazole, phoxim, diniconazole, sethoxydim, temephos, tetrachlorvinphos, pendimethalin, boscalid, disulfoton sulfone, lenacil, propiconazole, cycloxydim, pyridaben, and terbuthylazine. Amitrole, diniconazole, and tebuconazole were found to be common in all three lakes. Lakes Kerkini and Doirani exhibited increased concentrations during the first sampling period (winter 2010) with predominant pesticide classes, triazines/triazoles and organophosphates. Pollution is mainly located near the populated villages of the lakes and the nearby cultivations. During the second sampling period, pesticide concentrations appear lower and located in sediments near the center of the lake. Lake Volvi exhibits increased pesticide concentrations during the second sampling period, temporal and spatial variations and different pesticide profile pattern. Increased pollution occurs near the center of the lake during the first sampling period, mainly comprised by triazines/triazoles and organophosphates. During the second sampling period, the majority of the sediment samples demonstrated a different pesticide profile dominated by unclassified pesticides and triazines/triazoles. Mineralogical analysis of the samples demonstrates that sediments are mainly composed of clay, mud, and sand particles, and they present spatial variations. Near the center of the lakes, sediments appear to be more fine-grained with higher clay content and are more likely to adsorb pesticides.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Development of an SPME-GC-MS/MS method for the determination of pesticides in rainwater: laboratory and field experiments

A solid-phase microextraction -- coupled to a gas chromatography -- ion trap tandem mass spectrometry (SPME-GC-MS/MS) method was developed for the quantitative determination in rainwater of 8 pesticides amongst the most used in France and 3 triazines metabolites. The main factors affecting the SPME process were studied. Using a 3 mL sample, the method developed showed good linearity for concentrations ranging from 0.05 to 50 microgL(-1) with correlation coefficients between 0.997 and 0.9999 and relative standard deviations (% RSD) below 14%. The study of matrix effects showed that rainwater was too diluted to have any significant influence on the extraction efficiency. To validate the method, a field campaign was carried out on the rain events, which occurred in Strasbourg during a one-year period. The rain concentrations showed patterns of high pesticide concentrations during spring months, which were correlated to the spraying periods of most of these substances.     

Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application

Intensive pesticide use leads to the contamination of water, soil and atmosphere. Atmospheric transport is responsible for pesticide dispersal over long distances. In this study, we evaluate the local dispersal of pesticides from agricultural to urban areas. For this purpose, three high-volume samplers, each equipped with a glass fiber filter and XAD-2 resin for the sampling of particulate and gas phase have been placed in a south-west transect (predominant wind direction) characteristic of rural and urban areas. The urban site (Strasbourg centre) is situated in the middle of two rural sites. Samples were taken simultaneously at three sites during pesticide treatments in autumn and spring 2002–2003. Sampling took place for 24 h at a flow rate of 10–15 m³ h⁻¹. The pesticides studied were those commonly used in the Alsace region for all crops (maize, cereal, vines …). Many of the pesticides analysed in atmospheric samples were not detected or observed very episodically at very low concentrations. For metolachlor, alachlor, trifluralin, atrazine and diflufenican, higher concentrations were observed, essentially during the application of these compounds. Moreover, some “spraying peaks” were observed for alachlor in the south rural site (near crops) at a level of 31 ng m⁻³ on 16–17 May 2003. These results show site and time dependence of atmospheric contamination by pesticides. A limited dispersal was also observed especially in the urban area during the application periods of pesticides.     

Phosphorus fractionation in lake sediments--lakes Volvi and Koronia, N. Greece

Sediments from two lakes, the meso-to-eutrophic Volvi and the hypertrophic Koronia, located in N. Greece were examined on the basis of P-fractionation. In both lakes, the rank order of P-fractions was HCl-P > NaOH-P > BD-P > NH4Cl-P. The loosely sorbed phosphorus (NH4Cl-P) represented < 1% of the sedimentary inorganic phosphorus, while the reductant phosphorus (BD-P) ranged 5-6%. The calcium bound phosphorus (HCl-P) showed considerable contribution (59-74%) to the sedimentary inorganic P-loads. The metal oxide bound phosphorus (NaOH-P) was higher in the hypertrophic (30-35%) than in the meso-to-eutrophic system (19-28%). Fine-sized sediments exhibited significantly higher concentrations of HCl-P in Volvi and NH4Cl-P in Koronia. Sampling month had significant effect in variance of most P-fractions and other sediment features in both lakes. Use was also made of multivariate statistics to identify the factors which influence the sedimentary phosphorus. NaOH-P was the most reactive fraction in Lake Volvi. Iron compounds and organic matter seem to play a significant role in regulating this labile P-budget. NH4Cl-P was the more reactive fraction in Lake Koronia which was influenced by sedimentation of P-absorbed on clay/silt fine particles.     

Assessing pesticide concentrations and fluxes in the stream of a small vineyard catchment - Effect of sampling frequency

This study reports on the occurrence and behaviour of six pesticides and one metabolite in a small stream draining a vineyard catchment. Base flow and flood events were monitored in order to assess the variability of pesticide concentrations according to the season and to evaluate the role of sampling frequency on the evaluation of fluxes estimates. Results showed that dissolved pesticide concentrations displayed a strong temporal and spatial variability. A large mobilisation of pesticides was observed during floods, with total dissolved pesticide fluxes per event ranging from 5.7 × 10⁻³ g/Ha to 0.34 g/Ha. These results highlight the major role of floods in the transport of pesticides in this small stream which contributed to more than 89% of the total load of diuron during August 2007. The evaluation of pesticide loads using different sampling strategies and method calculation, showed that grab sampling largely underestimated pesticide concentrations and fluxes transiting through the stream.     

Pesticide levels in surface waters in an agricultural-forestry basin in Southern Chile

Residues of five pesticides in surface water were surveyed during 2001 and 2003 in the Traiguen river basin in Southern Chile. Simazine, hexazinone, 2,4-D, picloram herbicides and carbendazim fungicide were selected through a pesticide risk classification index. Six sampling stations along the river were set up based on agricultural and forestry land use. The water sampling was carried out before and after the pesticide application periods and in correspondence to some rain events. Pesticides were analyzed by HPLC with DAD detection in a multiresidue analysis. During 2001, in the first sampling campaign (March), the highest concentrations of pesticides were 3.0 microg l(-1) for simazine and hexazinone and 1.8 microg l(-1) for carbendazim. In the second sampling (September), the highest concentration were 9.7 microg l(-1) for 2,4-D, 0.3 microg l(-1) for picloram and 0.4 microg l(-1) for carbendazim. In the last sampling period (December), samples indicated contamination with carbendazim fungicide at levels of up to 1.2 microg l(-1). In sampling carried out on May 2003, no pesticides were detected. In October 2003, the highest concentrations of pesticides were 4.5 microg l(-1) for carbendazim and 2.9 microg l(-1) for 2,4-D. Data are discussed in function of land use and application periods of the products, showing a clear seasonal pattern pollution in the Traiguen river. Risk assessment for these pesticides was calculated by using a risk quotient (RQ = PNEC/PEC). For picloram the calculated RQ < was 0, which indicates that no adverse effects may occur due to the exposure to this herbicide in the Traiguen river basin. For 2,4-D, simazine, hexazinone, carbendazim RQ > 1, meaning that adverse effects could occur and it is necessary to reduce pesticide exposure in surface waters. It is recommended to continue with a pesticide monitoring program and the implementation of ecotoxicological testing with local and standardized species in order to consider the probability of effects occurrence, with less uncertainty. Thus, it will be more feasible to make some recommendations to regulatory agencies regarding the pesticide use.     

Occurrence of priority organic pollutants in Strymon river catchment, Greece: inland, transitional, and coastal waters

Twenty-five sampling stations were selected in order to monitor persistent organic pollutants (polycyclic aromatic hydrocarbons (PAHs), organochlorine (OC) pesticides and total polychlorinated biphenyls (PCBs)) in surface water from Kerkini Lake, the Strymon River, its main tributaries and estuary in N. Aegean Sea during January to July, 2008, according to recent European Union (EU) guidelines. The data were divided among the high (January to April) and the low flow season (May to July). Generally, the values for organic pollutants were within the range reported worldwide for surface water. Elevated PAHs concentrations were observed compared with other places in Greece. Anthracene and benzo(a)pyrene exceeded maximum allowable concentration (MAC) of the relative EU guideline. Also, concentrations above MAC were observed for OCs, γ-HCH, and a-endosulfan. Despite the fact that it is banned since 1972, Aldrin was detected during the monitoring season (from limit of detection (LOD) to 15 ng L(-1)). Total PCB concentrations ranged from LOD to 162 ng L(-1). In addition, the load of organic pollutants was estimated in April (high flow) and June (low flow) in selected sampling stations. According to this estimation, napthalene, anthracene, and fluoranthene (PAHs), total dichlorodiphenyltrichloroethane (DDT), aldrin, and total PCBs had the highest load. Taking into account the relative EU guidelines concerning the pollutants studied, the water quality in the Strymon River catchment could be characterized as poor, which can lead to negative impacts to its biota.     

Temporal variations of concentrations of currently used pesticides in the atmosphere of Strasbourg, France

Atmospheric samples have been collected in Strasbourg between April 18 and May 29, 2007 and were analyzed for 71 current-use pesticides, of which 38 were detected. Average concentrations ranged from 0.09 ng m⁻³ for Fenarimol to 110.42 ng  m⁻³ for Dimethachlor, which was slightly higher than the concentrations reported from other, comparable agricultural regions.Significant temporal variations were observed for 30 pesticides, and for most of them it could be shown that these were linked to time, temperature or atmospheric pressure. In several cases this helped to identify pesticide application just before or at the beginning of the sampling period, or ongoing treatment. Humidity, in contrast to previous reports, could not be linked to these variations. For the other 8 pesticides, only very little temporal variations were observed. Generally, these concentrations were low (less than 1 ng m⁻³), and it was assumed that they are not in use in Alsace at present.     

Plant uptake of pesticides and human health: dynamic modeling of residues in wheat and ingestion intake

Human intake of pesticide residues from consumption of processed food plays an important role for evaluating current agricultural practice. We take advantage of latest developments in crop-specific plant uptake modeling and propose an innovative dynamic model to estimate pesticide residues in the wheat-environment system, dynamiCROP. We used this model to analyze uptake and translocation of pesticides in wheat after foliar spray application and subsequent intake fractions by humans. Based on the evolution of residues in edible parts of harvested wheat we predict that between 22 mg and 2.1 g per kg applied pesticide are taken in by humans via consumption of processed wheat products. Model results were compared with experimentally derived concentrations in wheat ears and with estimated intake via inhalation and ingestion caused by indirect emissions, i.e. the amount lost to the environment during pesticide application. Modeled and measured concentrations in wheat fitted very well and deviate from less than a factor 1.5 for chlorothalonil to a maximum factor 3 for tebuconazole. Main aspects influencing pesticide fate behavior are degradation half-life in plant and time between pesticide application and crop harvest, leading to variations in harvest fraction of at least three orders of magnitude. Food processing may further reduce residues by approximately 63%. Intake fractions from residues in sprayed wheat were up to four orders of magnitude higher than intake fractions estimated from indirect emissions, thereby demonstrating the importance of exposure from consumption of food crops after direct pesticide treatment.     

Persistent organochlorine pesticide residues in fish, sediments and water from Lake Bosomtwi, Ghana

Some organochlorine pesticide residues in tilapia fish (Tilapiazilli), sediment and water samples from Lake Bosomtwi (the largest natural lake in Ghana) were determined to find out the extent of pesticide contamination and accumulation in the lake. The extracted residues were analyzed on a micro-capillary gas chromatograph equipped with electron capture detector. DDE (p,p'-1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene) was the predominant residue in all the samples analyzed; detected in 82% of water samples, 98% of sediment samples and 58% of fish samples at concentrations of 0.061+/-0.03 ng g(-1), 8.342+/-2.96 ng g(-1) and 5.232+/-1.30 ng g(-1), respectively. DDT (p,p'-1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane) was detected in 78% at a mean concentration 0.012+/-0.62 ng g(-1) of water samples analyzed. The mean concentrations of DDT in sediments and fish were 4.41+/-1.54 ng g(-1) and 3.645+/-1.81 ng g(-1), respectively. The detection of lower levels of DDT than its metabolite, DDE, in the samples implies that the presence of these contaminants in the lake is as result of past usage of the pesticides.     

Pesticides in precipitation in the Gdańsk region (Poland)

Selected organonitrogen, organophosphorus and organochlorine pesticides have been determined in precipitation samples collected at 10 sites in the Gdańsk region (northern Poland) over a period of one year (1998). Compounds which were detected most often included simazine (0.11-5.80 ng/l), fenitrothion (0.1-2.10 ng/l), chlorfenvinfos (0.1-1.30 ng/l), gamma-HCH (0.012-5.06 ng/l), heptachlor epoxide (0.05-3.28 ng/l) and aldrin (0.02-3.28 ng/l). The pesticide concentrations in precipitation samples revealed seasonal fluctuations, with higher concentrations observed during the application periods (June and July). The concentrations observed were also affected by the inflow of polluted air masses from the southwest. The total pesticide concentration in the precipitation samples was strongly related to the abundance of green areas in the vicinity of the sampling sites. A weak correlation was also found between the total concentration of organonitrogen and organophosphorus pesticides, and the total concentration of organochlorine pesticides in the samples collected.     

Effects of soil composition on solid phase microextraction determination of triazine and organophosphorus pesticides

The influence of organic matter and clay contents on headspace solid phase microextraction (HS-SPME) determination of triazine and organophosphorus pesticides in different soils was studied. The results of the study showed that content of soil organic matter dominantly participated in sorption of triazines (simazine, atrazine and prometryn) to soil, while sorption of organophosphorus pesticides (phorate and tebupirimfos) could not be explained only by contents of dominant soil sorption components (soil organic matter and clay). Sorption of all pesticides studied to different soil types was similar at their lower concentrations while the influence of soil composition was expressed at higher concentration levels. Except for phorate, the obtained sorption trends were different from those obtained by direct SPME mode (DM-SPME) and exhaustive liquid-solid extraction (LSE) method. These results indicated that most likely co-extractants from the analyzed medium complicated evaporation and diffusion of the pesticides to the PDMS fiber during HS-SPME sampling.     

The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels

This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides. Rivers were found to be more polluted than lakes. The detected concentrations of most pesticides follow a seasonal variation, with maximum values occurring during the late spring and summer period followed by a decrease during winter. Nationwide, in many cases the reported concentrations ranged in low ppb levels. However, elevated concentrations were recorded in areas of high pesticide use and intense agricultural practices. Generally, similar trends and levels of pesticides were found in Greek rivers compared to pesticide contamination in other European rivers. Monitoring of the Greek water resources for pesticide residues must continue, especially in agricultural regions, because the nationwide patterns of pesticide use are constantly changing. Moreover, emphasis should be placed on degradation products not sufficiently studied so far.     

Pesticide concentrations in agricultural storm drainage inlets of a small Swiss catchment

Agricultural pesticides transported to surface waters pose a major risk for aquatic ecosystems. Modelling studies indicate that the inlets of agricultural storm drainage systems can considerably increase the connectivity of surface runoff and pesticides to surface waters. These model results have however not yet been validated with field measurements. In this study, we measured discharge and concentrations of 51 pesticides in four out of 158 storm drainage inlets of a small Swiss agricultural catchment (2.8 km²) and in the receiving stream. For this, we performed an event-triggered sampling during 19 rain events and collected plot-specific pesticide application data. Our results show that agricultural storm drainage inlets strongly influence surface runoff and pesticide transport in the study catchment. The concentrations of single pesticides in inlets amounted up to 62 µg/L. During some rain events, transport through single inlets caused more than 10% of the stream load of certain pesticides. An extrapolation to the entire catchment suggests that during selected events on average 30 to 70% of the load in the stream was transported through inlets. Pesticide applications on fields with surface runoff or spray drift potential to inlets led to increased concentrations in the corresponding inlets. Overall, this study corroborates the relevance of such inlets for pesticide transport by establishing a connectivity between fields and surface waters, and by their potential to deliver substantial pesticide loads to surface waters.

     

Pentachlorophenol (PCP), PCDD,PCDF and pesticide concentrations in a freshwater lake catchment

The concentrations of pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins (PCDDs) polychlorinated dibensofurans (PCDFs) and organochlorine and organophosphorus pesticides in water, sediments and biota from the Lake Rotorua catchment were determined to evaluate the relative significance of various contaminants and their potential sources. PCP was found in water, sediments and biota (fish and freshwater mussels) and the highest concentrations in water (3.62 μ g.L⁻¹) and in sediments (400 ng.g⁻¹ dry weight (DW) were found in and near a stream that had been affected by PCP contamination from a sawmill. PCDD and PCDF concentrations in all cases, except for the waters and sediments of the stream near to the sawmill, were relatively low compared to values reported in the literature for similar sites. Negligible pesticide contamination was found in the Lake Rotorua catchment. Pesticides found included low concentrations of p.p′-DDE, p.p-TDE and dieldrin in rainbow trout from the lake.     

Possible alkylation of inorganic Hg(II) by photochemical processes in the environment

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L⁻¹, respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L⁻¹, were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.     

Organochlorine contaminants in the estuarine and coastal marine environments of the Fiji Islands

No information has been published on the presence of organochlorine pesticides and polychlorinated biphenyls in the Fiji Islands. This paper reports the first data on the concentration of a range of organochlorine compounds in sediments and shellfish in the estuarine and coastal marine environment around Fiji. Twenty-three sediment and two shellfish samples were analysed for 22 pesticides and related residues, and PCBs. While a significant number of organochlorines (20 pesticide related species and PCBs) was detected, the concentrations were generally very low (< 10 ng g), indicative of a relatively 'less contaminated' marine environment. Relatively high concentrations were observed only near the two major ports (Suva and Lautoka), with Suva harbour samples having the largest number of detectable species and the largest total concentrations of organochlorines (up to 91 ng g). No PCBs were detected in areas away from major industrial centres. The variations in the concentrations found, and the possible sources and movement of the organochlorine contaminants are discussed.     

Comparison of atmospheric concentrations of currently used pesticides between urban and rural areas during intensive application period in Alsace (France) by using XAD-2® based passive samplers

XAD-2® passive samplers (PAS) have been exposed simultaneously for 14 days on two sites, one rural and one urban, situated in Alsace (East of France) during intensive pesticides application in agriculture (between March and September). PAS have been extracted and analyzed for current-used pesticides and lindane with an analytical method coupling accelerated solvent extraction (ASE), solid-phase microextraction (SPME) and GC/MS/MS. Results show the detection of pesticides is linked to the period of application and spatial and temporal variabilities can be observed with these PAS during the selected sampling period. The spatial and temporal variability is comparable to the one previously observed by comparing data obtained with PAS with data from Hi.-Vol. samplers in an urban area. Sampling rates were calculated for some pesticides and values are comparable to the data already available in the literature. From these sampling rates, concentrations in ng m^?3 of pesticides in PAS have been calculated and are in the same order of magnitude as those obtained with Hi.Vol. sampling during the same period of time.     

pp´DDT and pp´DDE Accumulation in a Food Chain of Lake Maggiore (Northern Italy): Testing Steady-State Condition

- DOI: http://dx.doi.org/10.1065/espr2006.01.010 Background, Aims and Scope Although pp'DDT usage was strongly limited or banned in most parts of the world during the last three or four decades, the parent compound, its homologues and their metabolites still occur at levels which might pose a risk for many ecosystem components. A case of DDT pollution of industrial origin was discovered in 1996 in Lake Maggiore, the second largest (212 km2) and deepest (370 m) lake in Italy, causing concern for wildlife and human health. The extensive monitoring of many biotic and abiotic compartments which followed from 1998 in order to assess the pollution level and its trend in time, provided a great availability of data referring to DDT contamination of the different fish species of the lake. In this study, the recent contamination levels in selected fish species were compared to those measured in 1998 to evaluate the temporal pollution trend of the lake and its natural recovery, given that no remediation measures were carried out on the contaminated soils and sediments in this time span. Moreover, a modelling approach to test the equilibrium condition between water and pelagic fish species was used. Analytical results of pp'DDT and pp'DDE concentrations in lake water were used as input data in the bioenergetic model by Connolly & Pedersen (1988) to calculate concentrations in two fish species and to compare the predicted and the measured contamination. Methods Sampling and analytical determination of DDT homologues in lake water: Five water sampling campaigns were carried out from May 2002 to February 2004 in three sampling sites of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Quantitative DDT homologue analyses were performed by HRGC coupled with ECD detection by the external standard method. Single water extracts were put together in correspondence with the stratification zones of the water column inferred on the basis of the temperature profile to improve analytical sensitivity. Selection of fish data: Concentrations of DDT and DDE in fishes were selected from recent literature (CIPAIS 2003, 2004). Bioaccumulation model: The bioenergetic model proposed by Connolly & Pedersen (1988) was used to assess the bioaccumulation of pp'DDT and pp'DDE of Alosa fallax (landlocked shad) and Coregonus spp. (whitefish), selected among the different species as representative of a secondary consumer level. Results and Discussion The average concentrations of pp'DDT and pp'DDE in water to be used as input data in the bioenergetic model were obtained considering all the concentrations measured at the three sampling stations in the epylimnion where the fish species considered in this study spend most of their life. The resulting values were 0.05 and 0.16 ng/L for pp'DDT and pp'DDE, respectively. Average measured pp'DDT and pp'DDE concentrations in landlocked shad were 0.81 +/- 0.39 and 1.69 +/- 0.71 mg/kg lipids, respectively, and were 0.29 +/- 0.12 and 1.06 +/- 0.41 mg/kg lipids for the whitefish. Calculated and measured values turned out to be in quite good agreement for pp'DDT, while measured pp'DDE concentrations were higher than expected on the basis of the bioenergetic model in both species. Probably metabolic transformations of pp'DDT accumulated in fish tissues in the past are responsible for the observed differences between calculated and expected pp'DDE concentrations in fish. Conclusions Pelagic fishes of Lake Maggiore seem to maintain the DDT accumulated during their life time and the most efficient mechanism responsible for the fish population recoveries is probably their generation changes; for this reason, equilibrium models cannot be used until negligible pp'DDT concentrations are reached in fish tissues. Recommendations and Outlook The limit proposed for pp'DDT in water by the EU Directive 2000/60, which will come in force in 2008, is 0.2 ng/L, four times higher than the average concentration measured in Lake Maggiore waters. Nevertheless, concentrations measured in Lake Maggiore fish were very close and sometimes exceeded the Maximum residue limits (MRLs) settled by the Italian legislation for foods (0.1 mg/kg w.w. for fish containing 5–20% lipid). It seems, therefore, that the 'environmental quality standard' of 0.2 ng/L cannot guarantee the suitability of fish for human consumption.