Pesticides detected in surface and groundwater from agroecosystems in the Pampas region of Argentina: occurrence and ecological risk assessment.

The objective of this study was to evaluate the occurrence of pesticides in surface and groundwater of agricultural areas of the Pampas region of Argentina and to develop an ecological risk assessment (ERA) of pesticides in freshwater ecosystems. Eight agricultural sites from south Santa Fe province, in the north of the Pampas region, were sampled seven times between 2016 and 2018. Pesticides were analysed by gas chromatography-mass spectrometry (GC/MS) and liquid chromatography-mass spectrometry (UPLC-LC/MS). Twenty compounds among herbicides, insecticides and fungicides in 84% and 79% of groundwater and surface water samples, respectively, were detected. Atrazine was the most ubiquitous pesticide, following by metolachlor, acetochlor and glyphosate, with maximum concentrations of 28, 24, 77 and 111 µg/L, respectively. An ERA was performed by employing the risk quotient (RQ) method. Atrazine, azoxystrobin, pirimiphos-methyl, acetochlor and epoxiconazole posed a high and very high risk for aquatic organisms (RQ > 1) and glyphosate, metolachlor and 2,4-D exhibited negligible to medium risk. The herbicides were the major contributors to risk. This study is the first contribution on the presence and concentration of pesticides in surface and groundwater from agricultural areas of south Santa Fe province, north Pampas region, Argentina, and a starting point for pesticide ecological risk assessment.

Pirimicarb-based formulation-induced genotoxicity and cytotoxicity in the freshwater fish Cnesterodon decemmaculatus (Jenyns, 1842) (Pisces, Poeciliidae).

We analyzed the aspects of lethality, genotoxicity, and cytotoxicity in the ten spotted live-bearer exposed under laboratory conditions to the pirimicarb-based formulation Patton Flow® (50% active ingredient (a.i.)). Acute effects were evaluated using different end points for lethality, genotoxicity, and cytotoxicity. Median lethal concentration (LC50) estimation was employed as a bioassay for lethality, whereas micronucleus (MN) induction and alterations in erythrocyte/erythroblast frequency were used as end points for genotoxicity and cytotoxicity, respectively. Results demonstrated an LC5096h value of 88 mg/L. Patton Flow® increased the MN frequency in fish erythrocytes after 48 h of exposure at a concentration of 66 mg/L, whereas a concentration range of 22-66 mg/L was able to exert the same genotoxic effect at 96 h of treatment. Furthermore, cytotoxicity was also observed by alterations in erythrocyte/erythroblast frequencies within the concentration range of 22-66 mg/L, regardless of the exposure time. Our current observations provide evidence that Patton Flow® (50% a.i.) should be considered a clear lethal, cytotoxic, and genotoxic agent on Cnesterodon decemmaculatus. Thus, repeated applications of this carbamic insecticide can enter the aquatic environment and exert deleterious effects on aquatic organisms other than the evaluated species C. decemmaculatus.

Chlorpyrifos-based insecticides induced genotoxic and cytotoxic effects in the ten spotted live-bearer fish, Cnesterodon decemmaculatus (Jenyns, 1842).

Mortality, genotoxicity, and cytotoxicity of the 48% chlorpyrifos (CPF)-based formulations Lorsban* 48E(®) and CPF Zamba(®) were evaluated on Cnesterodon decemmaculatus (Jenyns, 1842) (Pisces, Poeciliidae) under laboratory conditions. Induction of micronucleus (MN) and alterations in the erythrocyte/erythroblast frequencies were employed as end points for genotoxicity and cytotoxicity, respectively. For Lorsban* 48E(®) , mean values of 0.13 and 0.03 mg/L were determined for LC50 at 24 and 96 h, respectively, and these concentrations reached mean values of 0.40 and 0.21 mg/L for CPF Zamba(®) . Mortality values increased as a positive linear function of the CPF Zamba(®) concentrations, but not for Lorsban* 48E(®) concentrations. There was no significant relationship between mortality and exposure time within the 0-96 h period for both formulations. LC50 values indicated that the fish were seven fold more sensitive to Lorsban* 48E(®) than to CPF Zamba(®) . Lorsban* 48E(®) within the concentration range of 0.008-0.025 mg/L increased MN frequency at both 48 and 96 h of treatment. Similar results were also observed when fish were exposed to 0.052-0.155 mg/L of CPF Zamba(®) , regardless of the exposure time. Cellular cytotoxicity was found after Lorsban* 48E(®) and CPF Zamba(®) treatments for all concentrations and time exposures, estimated by a decrease in the frequency of mature erythrocytes and a concomitant enhanced frequency of erythroblasts in circulating blood. Furthermore, our results demonstrated that Lorsban* 48E(®) and CPF Zamba(®) should be considered as CPF-based commercial formulations with marked genotoxic and cytotoxic properties.

Single-cell gel electrophoresis assay in the ten spotted live-bearer fish, Cnesterodon decemmaculatus (Jenyns, 1842), as bioassay for agrochemical-induced genotoxicity.

The ability of two 48 percent chlorpyrifos-based insecticides (Lorsban* 48E® and CPF Zamba®), two 50 percent pirimicarb-based insecticides (Aficida® and Patton Flow®), and two 48 percent glyphosate-based herbicides (Panzer® and Credit®) to induce DNA single-strand breaks in peripheral blood erythrocytes of Cnesterodon decemmaculatus (Jenyns, 1842) (Pisces, Poeciliidae) exposed under laboratory conditions was evaluated by the single-cell gel electrophoresis (SCGE) assay. In those fish exposed to Lorsban* 48E®, CPF Zamba®, Aficida®, Patton Flow®, Credit®, and Panzer®, a significant increase of the genetic damage was observed for all formulations regardless of the harvesting time. This genotoxic effect was achieved by an enhancement of Type II-IV comets and a concomitant decrease of Type 0-I comets over control values. A regression analysis revealed that the damage varied as a negative function of the exposure time in those Lorsban* 48E®- and Aficida®-treated fish. On the other hand, a positive correlation between damage increase and exposure time was achieved after Patton Flow® and Credit® treatment. Finally, no correlation was observed between increase in the genetic damage and exposure time after treatment with CPF Zamba® or Panzer®. These results highlight that all agrochemicals inflict primary genotoxic damage at the DNA level at sublethal concentrations, regardless of the exposure time of the aquatic organisms under study, at least within a period of 96 h of treatment.

Evaluation of the genotoxic and cytotoxic effects of glyphosate-based herbicides in the ten spotted live-bearer fish Cnesterodon decemmaculatus (Jenyns, 1842).

Mortality, genotoxicity, and cytotoxicity of the 48% glyphosate-based formulations Panzer and Credit(®) were evaluated on Cnesterodon decemmaculatus (Jenyns, 1842) (Pisces, Poeciliidae) under laboratory conditions. Induction of micronuclei (MN) and alterations in the erythrocytes:erythroblasts ratio were employed as end points for genotoxicity and cytotoxicity, respectively. For Panzer(®), mean values of 16.70 and 15.68 mg/L were determined for LC(50) at 24 and 96 h, respectively, and these concentrations reached mean values of 98.50 and 91.73 mg/L for Credit(®). LC(50) values decreased as a negative linear function of Panzer(®) exposure time within the 0-96 h period, but not for Credit(®). LC(50) values indicated that the fish were more sensitive to Panzer(®) than to Credit(®). Both 3.9 and 7.8 mg/L of Panzer(®) increased MN frequency at 48 and 96 h of treatment. When fish were exposed to Credit(®), an increased frequency of MN over control values was found after 96 h for all concentrations assayed, but not after 48 h. No cellular cytotoxicity was found after Panzer(®) and Credit(®) treatment, regardless of both the concentration and the sampling time. Furthermore, our results demonstrated that Panzer(®) and Credit(®) should be considered as glyphosate-based commercial formulations with genotoxic but not cytotoxic effect properties.

Sublethal and lethal effects on Rhinella arenarum (Anura, Bufonidae) tadpoles exerted by the pirimicarb-containing technical formulation insecticide Aficida.

Acute toxicity, genotoxicity, and cytotoxicity of the pirimicarb-containing commercial-formulation carbamate insecticide Aficida(R) (50% pirimicarb) were evaluated on Rhinella arenarum (Anura, Bufonidae) tadpoles exposed under laboratory conditions. Lethal and sublethal effects were employed as bioassays for acute toxicity, whereas micronuclei (MNi) induction and alterations in the ratio erythrocytes:erythroblasts were employed as end-points for genotoxicity and cytotoxicity, respectively. Cr(VI) (23 mg L(-1)) and cyclophosphamide (40 mg L(-1)) were employed as positive controls for toxicity and geno-cytotoxicity assays, respectively. In Gosner stage 25 (STD25), the results revealed mean values of 402.0 and 223.6 mg Aficida L(-1) for LC-50(24)(h) and LC-50(96)(h), respectively. When STD37-39 tadpoles were exposed, the LC-50(24)(h) and LC-50(96)(h) reached values of 239.4 and 181.7 mg Aficida L(-1), respectively. Sublethal effects revealed a mean EC-50(96)(h) of 133.85 and 104.2mg Aficida in those STD25 and STD37-39 treated tadpoles, respectively. The results demonstrated that in 48-h-exposed tadpoles, a MNi increase was found only in those 80.0 mg L(-1) Aficida-treated individuals. When tadpoles were exposed to Aficida for 96h, only the 160 mg L(-1)-treated individuals showed a significant increase in MNi frequency. Concentrations ranging from 80.0 to 250.0mg Aficida L(-1) resulted in cellular cytotoxicity, revealed by a decreased proportion of circulating erythrocytes and an enhancement of erythroblasts. Accordingly, this species could provide a suitable and useful experimental model for biomonitoring aquatic ecosystems.