Spatial and temporal analysis of pesticides concentrations in surface water: pesticides atlas

Dutch water boards have a well-established program for monitoring pesticide contamination of surface waters. These monitoring data have been processed into a graphic format accessible online and designed to provide insight into pesticide presence in Dutch surface waters and trends over time: the Pesticides Atlas (http://www.pesticidesatlas.nl). With this tool one can easily get maps of where a pesticide is being measured and where it might possibly constitute an environmental problem over the years. Presently, results of the periods 1997/1998 until 2005/2006 are available at the level of individual active ingredients. At a national level, the percentage of pesticides concentrations that exceed the maximum tolerable risk has declined 30% to 38% over the years 2003/2004 compared with 1997/1998. This means that surface water quality in the Netherlands has improved with respect to pesticides, however there are still many locations at which the measured concentrations exceed the environmental quality standards. The results on linking land use to pesticides concentrations were shown to assist in optimization of monitoring programs. By developing the present Internet tool, many new opportunities for environmental risk assessment and risk management were identified, e.g. optimization of monitoring strategies and communication to policymakers.     

Raman and SERS spectra of thiamethoxam and the Ag3–thiamethoxam complex: an experimental and theoretical investigation

Dutch water boards have a well-established program for monitoring pesticide contamination of surface waters. These monitoring data have been processed into a graphic format accessible online and designed to provide insight into pesticide presence in Dutch surface waters and trends over time: the Pesticides Atlas (http://www.pesticidesatlas.nl). With this tool one can easily get maps of where a pesticide is being measured and where it might possibly constitute an environmental problem over the years. Presently, results of the periods 1997/1998 until 2005/2006 are available at the level of individual active ingredients. At a national level, the percentage of pesticides concentrations that exceed the maximum tolerable risk has declined 30% to 38% over the years 2003/2004 compared with 1997/1998. This means that surface water quality in the Netherlands has improved with respect to pesticides, however there are still many locations at which the measured concentrations exceed the environmental quality standards. The results on linking land use to pesticides concentrations were shown to assist in optimization of monitoring programs. By developing the present Internet tool, many new opportunities for environmental risk assessment and risk management were identified, e.g. optimization of monitoring strategies and communication to policymakers.     

Effects of thiobencarb herbicide to an alga (Nannochloris oculata) and the cladoceran (Daphnia magna)

Chronic toxicity studies were conducted with an algae (Nannochloris oculata) and the cladoceran (Daphnia magna) to determine their relative sensitivities to the thiocarbamate herbicide thiobencarb (S-4-chlorobenzyl diethylthiocarbamate). Most of the algal populations were initially affected by exposure to the herbicide. Thiobencarb concentrations higher than 0.5 mg/L significantly reduced algal densities after 24-h exposure. The 24-h static EC50 in D. magna was 3.01 mg/L. The sublethal effects of 0.3, 0.37, 0.5, 0.75, and 1.5 mg/L of thiobencarb concentrations on the survival, reproduction, and growth of D. magna were monitored for 21 days. The parameters used to determined the effect of the herbicide on D. magna were mean total young per female; mean brood size; days to first brood; intrinsic rate of natural increase (r); growth; and survival. Reproduction was significantly reduced at thiobencarb concentrations of 0.30 mg/L and higher while survival was affected after exposure to 0.75 and 1.5 mg/L of the pesticide. The r value decreased with increasing concentrations of thiobencarb. Growth, as measured by body length, was depressed significantly after exposure to all herbicide concentrations tested.     

Effects of cadmium, copper, lead and zinc on growth, reproduction and survival of the earthworm Eisenia fetida (Savigny): Assessing the environmental impact of point-source metal contamination in terrestrial ecosystems

The earthworm Eisenia fetida (Annelida: Oligochaeta) was exposed to a geometric series of concentrations of cadmium, copper, lead and zinc in artificial soil using the OECD recommended protocol. Mortality, growth and cocoon production were measured over 56 days to determine LC50 and EC50 values. No observed effect concentrations (NOECs) were also estimated. Furthermore, the percentage of viable cocoons and number of juveniles emerging per cocoon was recorded. Cocoon production was more sensitive than mortality for all the metals, particularly cadmium and copper for which NOEC reproduction values were an order of magnitude lower than those for NOEC mortality. However, there was no significant effect of metals on the viability of cocoons. The weights of earthworms declined in all treatments (including the controls) during the experiment. This was probably due to the lack of suitable food in the OECD standard soil medium used. It was concluded that future experiments should include animal manure in the test medium. The LC50, EC50 and NOEC values determined in this study were compared with concentrations of metals in soils in the vicinity of a smelting works at Avonmouth, southwest England. The 14-day LC50 for zinc in Eisenia fetida was exceeded in soils covering an area of 75 km2 around the works, compared to 4.2 km2 for copper and 4.7 km2 for lead. Soil values for cadmium did not exceed the LC50 value anywhere in the region. Similar estimates of relative effects on reproduction confirmed that zinc is most likely to be responsible for the absence of earthworms from sites close to the Avonmouth works. However, the OECD standard test overestimated the potential effects of metals on populations, since earthworms can be found as close as 1 km from the smelting works. The discrepancy between test and field observations was probably due to the greater availability of the metals in the artificial soil.     

Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations,sampling season and location

In a year-round monitoring program (1998), pesticide composition and toxic potency of the mix of pollutants present in rainwater were measured. The goal of the study was to relate atmospheric deposition of toxic potency and pesticide composition to each other and to sampling period and local agricultural activity. Rainwater was collected in 26 consecutive periods of 14 days in a background location (BACK) and in two locations representative for different agricultural practices, i.e. intensive greenhouse horticulture (HORT) and flower bulb culture (BULB). Samples were chemically analyzed for carbamate (CARB), organophosphate (OP) and organochlorine (OC) pesticides and metabolites. Esterase inhibiting potency of rainwater extracts was measured in a specially developed bio-assay with honeybee esterases and was expressed as an equivalent concentration of the model inhibitor dichlorvos. Estrogenic potency of the extracts was measured in the ER-CALUX reporter gene assay and was expressed as an equivalent concentration of estradiol. Multivariate principal component analysis (PCA) techniques proved to be valuable tools to analyze the numerous pesticide concentrations in relation to toxic potency, sampling location, and sampling season. Pesticide composition in rainwater depended much more on sampling season than on sampling location, but differences between and were mainly attributed to local differences in agricultural practice. On average, the esterase inhibiting potency exceeded the maximum permissible concentration set for dichlorvos in The Netherlands, and was significantly higher in than in and . Esterase inhibition correlated significantly with OP and CARB concentrations, as expected given the working mechanism of these insecticides. The estrogenic potency incidentally exceeded NOEC levels reported for aquatic organisms and was highest in . Although estrogenic potency of rainwater correlated with OC concentrations, the ER-CALUX responses could not be attributed to any particular pesticides. Besides, the contribution of non-analyzed xeno-estrogens as alkylphenol(-ethoxylates) and bisphenol-A to the estrogenic potency of rainwater could not be excluded. Further research should focus on the chemical identification of estrogenic compounds in rainwater. In addition, more attention should be given to the ecological consequences of atmospheric deposition of individual pesticides and of total toxic potencies that regularly exceed environmental criteria for Dutch surface waters and/or toxic threshold values for aquatic organisms.     

Short-term effects of metals on the filtration rate of the zebra mussel Dreissena polymorpha

In order to study the short-term ecotoxicity of metals to the freshwater mussel Dreissena polymorpha, the effects of Cu, Zn and Cd on the filtration rate of this mussel were determined in laboratory experiments. Filtration rate was chosen as the endpoint, because it is a sensitive sublethal parameter compared to mortality and it is an important parameter given the ecological role D. polymorpha fulfills. The filtration rate was calculated from the decrease in algal concentration, fed to mussels in aquaria, containing different metal concentrations. The EC50 for Cu (41 microg litre(-1)) was lower than for Cd (388 microg litre(-1)) and Zn (1350 microg litre(-1)). The NOEC(accumulation) for the essential metal Zn was higher than for the essential metal Cu. Cadmium, a non-essential metal, was accumulated at all elevated water concentrations, so the NOEC(accumulation) was the concentration in the control water (<0.2 microg litre(-1)). All (no) effect concentrations found in this study were above the quality criteria set for metal concentrations in Dutch surface water, suggesting that the zebra mussel is sufficiently protected by these quality criteria.     

Individual and mixture toxicity of three pesticides; atrazine,chlorpyrifos, and chlorothalonil to the marine phytoplankton species Dunaliella tertiolecta

This study analyzed the toxicity of three pesticides (the herbicide atrazine, the insecticide chlorpyrifos and the fungicide chlorothalonil) individually, and in two mixtures (atrazine and chlorpyrifos; atrazine and chlorothalonil) to the marine phytoplankton species Dunaliella tertiolecta (Chlorophyta). A standard 96 h static algal bioassay was used to determine pesticide effects on the population growth rate of D. tertiolecta. Mixture toxicity was assessed using the additive index approach. Atrazine and chlorothalonil concentrations > or = 25 microg/L and 33.3 microg/L, respectively, caused significant decreases in D. tertiolecta population growth rate. At much higher concentrations (> or = 400 microg/L) chlorpyrifos also elicited a significant effect on D. tertiolecta population growth rate, but toxicity would not be expected at typical environmental concentrations. The population growth rate EC50 values determined for D. tertiolecta were 64 microg/L for chlorothalonil, 69 microg/L for atrazine, and 769 microg/L for chlorpyrifos. Atrazine and chlorpyrifos in mixture displayed additive toxicity, whereas atrazine and chlorothalonil in mixture had a synergistic effect. The toxicity of atrazine and chlorothalonil combined was approximately 2 times greater than that of the individual chemicals. Therefore, decreases in phytoplankton populations resulting from pesticide exposure could occur at lower than expected concentrations in aquatic systems where atrazine and chlorothalonil are present in mixture. Detrimental effects on phytoplankton population growth rate could impact nutrient cycling rates and food availability to higher trophic levels. Characterizing the toxicity of chemical mixtures likely to be encountered in the environment may benefit the pesticide registration and regulation process.     

Toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine to larval zebrafish (Danio rerio)

Hexahydro-1,3,5-trinitro-1,3,5-triazine, a cyclonitramine commonly known as RDX, is used in the production of military munitions. Contamination of soil, sediment, and ground and surface waters with RDX has been reported in different places around the world. Acute and subacute toxicities of RDX have been relatively well documented in terrestrial vertebrates, but among aquatic vertebrates the information available is limited. The objective of this study was to characterize the acute toxicity of RDX to larval zebrafish. Mortality (LC50) and incidence of vertebral column deformities (EC50) were two of the end points measured in this study. The 96-h LC50 was estimated at 22.98 and 25.64 mgl(-1) in two different tests. The estimated no-observed-effective-concentration (NOEC) values of RDX on lethality were 13.27+/-0.05 and 15.32+/-0.30 mgl(-1); and the lowest-observed-effective-concentration (LOEC) values were 16.52+/-0.05 and 19.09+/-0.23 mgl(-1) in these two tests, respectively. The 96-h EC50 for vertebral deformities on survivors from one of the acute lethality tests was estimated at 20.84 mgl(-1), with NOEC and LOEC of 9.75+/-0.34 and 12.84+/-0.34 mgl(-1), respectively. Behavioral aberrations were also noted in this acute toxicity study, including the occurrence of whirling movement and lethargic behavior. The acute effects of RDX on survival, incidence of deformities, and behavior of larval zebrafish occurred at the high end of the most frequently reported concentrations of RDX in aquatic environments. The chronic effects of RDX in aquatic vertebrates need to be determined for an adequate assessment of the ecological risk of environmental RDX.     

Application of the Microtox test and pollution indices to the study of water toxicity in the Albufera Natural Park (Valencia, Spain)

The toxic effects of waters collected from irrigation channels in a Mediterranean wetland (Albufera Natural Park, Valencia, Spain) were tested with the Microtox assay and compared with six pollution indices (PIs) defined from analytical parameters. Chemical oxygen demand (COD), biological oxygen demand (BOD), nutrients, heavy metals and pesticides were measured. The bioassay result (concentrations of the water sample (% V/V) that reduced light emission to 10%, 20% and 50%, EC10, EC20 and EC50, respectively (ECs)) was compared with the PIs. This comparison has demonstrated a general agreement between ECs and PIs, except in the case of irrigation channels affected by herbicides used in rice farming (molinate and thiobencarb). No pronounced inhibition was detected in the bioluminescence in relation to the eutrophic parameters in the irrigation waters for EC50 values, indicating that this parameter does not suffice to detect eutrophic waters. Data derived from irrigation water pollution and bioassay were assembled by multivariate statistical techniques (principal component analysis). These components were associated with various contamination sources.     

A new protocol to measure the effects of toxicants on daphnid-algae interactions

Inhibition of zooplankton grazing by toxicants present at sublethal concentrations in freshwater ecosystems can lead to uncontrolled algal growth and consequently exacerbate eutrophication problems. Short-term measurements of cladoceran grazing inhibition have been reported for some toxicants, but these studies do not mimic the actual interactions between microalgae, daphnids and toxicants, since algal growth is not allowed. On the opposite, algal blooms in complex microcosm or mesocosm assays have been interpreted as consequences on zooplankton, but effects on grazing, survival, growth or reproduction could not be easily discriminated. In this study, a simple assay with daphnids and microalgae is proposed to measure effects on grazing in dynamic conditions (algal growth over 6 days), and applied to copper and lindane. In the same time, direct effects on algal growth can be shown and taken into account. Results are compared with daphnid response measured with different endpoints (immobilization test and static grazing assay). For both toxicants, effects at sublethal concentrations were demonstrated. Copper impaired daphnid grazing at 10 microg/l (60% inhibition) in the 48 h-static test and 15 microg/l (40% inhibition) in the 6 day-dynamic test, whereas 48 h-EC50 for daphnid mobility was 47 microg/l. The EC50s for lindane were 50 microg/l for daphnid grazing (48 h-static and 6 day-dynamic tests) and 383 microg/l for the immobilization test (48 h).     

Effects of propanil, tebufenozide and mefenacet on growth of four freshwater species of phytoplankton: a microplate bioassay

The Albufera Natural Park situated in Valencia (Spain), with a very rich flora and fauna is surrounded by rice fields in which pesticide spraying is a regular practice. With this in mind, the sensitivity of four algal species, Scenedesmus acutus, Scenedesmus subspicatus, Chlorella vulgaris and Chlorella saccharophila to pesticides propanil, tebufenozide and mefenacet was studied using single species toxicity tests. Organisms were exposed to different concentrations of these herbicides and the algal growth was measured in a microplate reader at 410 nm, at 0, 24, 48 and 72 h. Tebufenozide appeared to be the most inhibitory to Scenedesmus and Chlorella species growth. 72 h EC50 of propanil, tebufenozide and mefenacet ranged from 0.29 to 5.98 mg/l, 0.12 to 0.15 mg/l and from 0.25 to 0.67 mg/l, respectively for the four algal species. The two species of Chlorella were more tolerant than the two species of Scenedesmus.     

Toxicity of chlorophenols to Pseudokirchneriella subcapitata under air-tight test environment

A closed-system algal toxicity test with no headspace was applied to evaluate the toxicity of chlorophenols to Pseudokirchneriella subcapitata. The dissolved oxygen production and the growth rate based on cell density were the response endpoints. Phenol and seven chlorophenols were tested using the above test technique. Median effective concentrations (EC50) range from 0.004 to 25.93 mg/l (based on DO production) and 0.0134 to 20.90 mg/l (based on growth rate). No-observed-effect concentration (NOEC) is within the range of 0.001-8.19 mg/l. In general, growth rate is a more sensitive response endpoint than the oxygen production, except for the case of pentachlorophenol. However, the differences in sensitivity between the two parameters were marginal. Furthermore, quantitative structure-activity relationships (QSAR's) based on the n-octanol/water partition coefficient (log P) and the acid dissociation constant (pK(a)) values were established with R(2) ranged from 0.90 to 0.96. From literature data also based on P. subcapitata, the new test method is 1.65-108 times more sensitive than the conventional algal batch tests. A completely different relative-sensitivity relationship among various aquatic organisms was thus observed. The results of this study indicate that the toxicity data of volatile organic chemicals derived by conventional algal toxicity tests may severely underestimate the impact of these toxicants. Our results show that alga is very sensitive to chlorophenols compared to other aquatic organisms such as the luminescent bacteria (the Microtox test), Daphnia magna, and rainbow trout.     

Effects of prevalent freshwater chemical contaminants on in vitro growth of Escherichia coli and Klebsiella pneumoniae

Many surface and ground waters in the continental US are contaminated with a variety of chemical pollutants, which are usually present in concentrations in the ppm and ppb range. The effects of these pollutants on coliform bacteria, which are prominent members of the aquatic flora, are poorly understood. Using a microtiter plate assay, isolates of Escherichia coli (from chicken intestine and fresh water), and an isolate of Klebsiella pneumoniae (from bovine milk) were exposed to varying concentrations of common pollutants over a 24 h period. The herbicides/pesticides simazine, atrazine, and diazinon; the VOCs trichloroethene and MTBE; the estrogens estradiol and estrone; and caffeine, all failed to inhibit bacterial growth at ppm levels. Only ethylene glycol, and the herbicide 2,4-D, significantly inhibited bacterial growth compared to controls. These results suggest that the replication of coliform bacteria in fresh waters is not adversely impacted by many common pollutants.     

Phytotoxicity and antioxidative enzymes of green microalga (Desmodesmus subspicatus) and duckweed (Lemna minor) exposed to herbicides MCPA, chloridazon and their mixtures

In this study, we evaluate the toxicity of MCPA (auxin-like growth inhibitor), chloridazon (CHD) (PSII-inhibitor) and their mixtures to floating plants and planktonic algae. Toxicity of MCPA (4-chloro-2-methylphenoxyacetic acid) and CHD (5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone) was first assessed in two growth inhibition tests with Lemna minor (ISO/DIS 20079) and Desmodesmus subspicatus (ISO 8692). Next, herbicide mixtures at concentrations corresponding to the EC values were used to assess their interactive effects, and the biomarkers were: for duckweed fresh weight, frond area, chlorophyll content and number of fronds, and for algae cell count and cell volume. The 3d EC?? and EC?? values using cell counts of D. subspicatus were 142.7 and 529.1 mg/L for MCPA and 1.7 and 5.1 mg/L for CHD. The 7d EC?? and EC?? values using frond number of L. minor amounted to 0.8 and 5.4 mg/L for MCPA and 0.7 and 10.4 mg/L for CHD. Higher sensitivity of reproductive (number of cells/fronds) than growth processes (cell volume/frond area) to herbicides applied individually and in mixtures was especially pronounced in the responses of Desmodesmus. Herbicide interactions were assessed by the two-way ANOVA and Abbott's formula. Generally, an antagonistic interaction with Lemna was revealed by MCPA and chloridazon, whereas additive effect of both herbicides was observed for Desmodesmus. A significant stimulation of SOD and APX activity by binary mixtures was noted in algal cells mainly after 24 and 48 hours of exposure. The extremely high stimulation of the activity of both enzymes was induced by the combination EC??CHD + EC??MCPA (48 h). Presumably due to oxidative stress, the treatment with CHD at concentration EC?? after 72 h was lethal for algae grown in aerated cultures, in contrast to standardized test conditions. Taking into account the consequences of risk assessment for herbicide mixtures we can state that a relatively low toxicity, as well as the lack of significant synergy between MCPA and CHD to non-target plants appears to be the most important result.     

Statistical analysis of regulatory ecotoxicity tests.

ANOVA-type data analysis, i.e.. determination of lowest-observed-effect concentrations (LOECs), and no-observed-effect concentrations (NOECs), has been widely used for statistical analysis of chronic ecotoxicity data. However, it is more and more criticised for several reasons, among which the most important is probably the fact that the NOEC depends on the choice of test concentrations and number of replications and rewards poor experiments, i.e., high variability, with high NOEC values. Thus, a recent OECD workshop concluded that the use of the NOEC should be phased out and that a regression-based estimation procedure should be used. Following this workshop, a working group was established at the French level between government, academia and industry representatives. Twenty-seven sets of chronic data (algae, daphnia, fish) were collected and analysed by ANOVA and regression procedures. Several regression models were compared and relations between NOECs and ECx, for different values of x, were established in order to find an alternative summary parameter to the NOEC. Biological arguments are scarce to help in defining a negligible level of effect x for the ECx. With regard to their use in the risk assessment procedures, a convenient methodology would be to choose x so that ECx are on average similar to the present NOEC. This would lead to no major change in the risk assessment procedure. However, experimental data show that the ECx depend on the regression models and that their accuracy decreases in the low effect zone. This disadvantage could probably be reduced by adapting existing experimental protocols but it could mean more experimental effort and higher cost. ECx (derived with existing test guidelines, e.g., regarding the number of replicates) whose lowest bounds of the confidence interval are on average similar to present NOEC would improve this approach by a priori encouraging more precise experiments. However, narrow confidence intervals are not only linked to good experimental practices, but also depend on the distance between the best model fit and experimental data. At least, these approaches still use the NOEC as a reference although this reference is statistically not correct. On the contrary, EC50 are the most precise values to estimate on a concentration response curve, but they are clearly different from the NOEC and their use would require a modification of existing assessment factors.     

Effects of methanol, ethanol and n-propanol on development of Artemia salina cysts

The current study proposes an ecotoxicological test that makes use of Artemia salina cyst; the results obtained made it possible to calculate the percentage of cyst mortality (no sign of development), and growth inhibition (a delay in normal development), as well as the percentage of larva malformation, and mortality. The dehydrated cysts were directly exposed for forty-eight hours to the action of three alcohols, methanol, ethanol, and n-propanol. No teratogenic or lethal effects on larvae were found at any methanol or ethanol concentrations. Predicted values of effect concentration, EC₁, EC₁₀ and EC₅₀ were calculated from the estimated probit models for larva growth inhibition, GI, and for cyst lethal concentration, LC. At concentrations of 0.21 M methanol and 0.13 M ethanol, there were no signs of alterations in Artemia salina cyst development; these concentrations show a NOEC (No Observed Effect Concentration) value, and properly employed do not interfere with effects due to a given chemical. The n-propanol was only used to verify the extreme resistance of the dried cysts to various environmental factors.     

Algal growth inhibition by river water pollutants in the agricultural area around Lake Biwa, Japan

An ecotoxicological study of river water discharged from the agricultural area around Lake Biwa was performed by using algal bioassays to guide chemical analysis. Water samples were collected once a week, at least, for 1 year starting in April 1997 and continuing until April 1998. The toxicities of the dissolved and particulate-adsorbed extracts of water samples were evaluated by the algal growth inhibition test and concentrations of individual pesticides were determined. Most of the river water that was collected during the periods when pesticides were applied to the paddy fields caused algal growth inhibition. Some extracts were found to contain herbicides (molinate, mefenacet, simetryn, or esprocarb) as major compounds. According to chemical assay and bioassay, simetryn was identified as the most toxic compound that caused algal growth inhibition.     

Mixture toxicity of the antifouling compound irgarol to the marine phytoplankton species Dunaliella tertiolecta

This study examined the toxicity of irgarol, individually and in binary mixtures with three other pesticides (the fungicide chlorothalonil, and the herbicides atrazine and 2,4-D), to the marine phytoplankton species Dunaliella tertiolecta. Standard 96-h static algal bioassays were used to determine pesticide effects on population growth rate. Irgarol significantly inhibited D. tertiolecta growth rate at concentrations > or = 0.27 micro g/L. Irgarol was significantly more toxic to D. tertiolecta than the other pesticides tested (irgarol 96 h EC50 = 0.7 micro g/L; chlorothalonil 96 h EC50 = 64 micro g/L; atrazine 96 h EC50 = 69 micro g/L; 2,4-D 96 h EC50 = 45,000 micro g/L). Irgarol in mixture with chlorothalonil exhibited synergistic toxicity to D. tertiolecta, with the mixture being approximately 1.5 times more toxic than the individual compounds. Irgarol and atrazine, both triazine herbicides, were additive in mixture. The toxicity threshold of 2,4-D was much greater than typical environmental levels and would not be expected to influence irgarol toxicity. Based on these interactions, overlap of certain pesticide applications in the coastal zone may increase the toxicological risk to resident phytoplankton populations.     

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.     

Detection limits can influence the interpretation of pesticide monitoring data in Canadian surface waters

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng⁻¹ L (range 0.39-25.1 ng⁻¹ L). We then simulated MDLs ranging from 25 to 1700 ng⁻¹ L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL < 1700 ng⁻¹ L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.