Behavior of ionophore antibiotics in aquatic environments in Argentina: The distribution on different scales in water courses and the role of wetlands in depuration.

We studied for the first time three ionophore anticoccidial drugs: monensin (MON), lasalocid (LAS), and salinomycin (SAL) as emerging pollutants originating from animal and plant husbandry in surface waters (n = 89) in one of the most extensive hydrological basins in South América (Del Plata basin). The soluble fraction of ionophores was pretreated by solid-phase extraction and analyzed by LC-MS/MS at a limit of detection of 1.7 ng·L-1. A statistical approach noted the need to report parameters calculated by methods based on the number of observations and the censorship percentage over substitution methods for more precise estimations of environmental data with a high percentage of left-censored data. Water collectors adjacent to intensive-husbandry facilities, placed in direct runoffs from animal excreta, or in wastewater emissions contained median concentrations of MON and SAL approximately 70 times higher than those found in regional tributaries and main courses of 5 sub-basins of the pampas and mesopotamic regions, thus exhibiting a relevance to other similar agricultural pollutants widely reported as pesticides. Chemical speciation of these compounds in surface water was characterized especially for MON and SAL, where the pH and chemical oxygen demand of the natural water body was associated with the concentration of the soluble fraction. The concentrations in abundant rivers such as the Gualeguay deliver a contribution to a natural wetland such as the Paraná-River delta, which registered only one sample with a [MON] ≤ the limit of quantification. Since wetlands possess a limited removal capability, these affluent contributions recorded strongly indicate that attention must be paid to the development of guidelines involving quality criteria for assessing the impact of ionophore antibiotics on such ecosystems.

Glyphosate and atrazine in rainfall and soils in agroproductive areas of the pampas region in Argentina.

The presence in the atmosphere of glyphosate (GLP) and atrazine (ATZ) was investigated-those pesticides dominating the market in Argentina-through rain, as the main climatic phenomenon associated with wet deposition, both through analyzing source-receptor relationships with soil along with the climatic influences that may condition that transport and through estimating the annual deposition on the surface of the Argentine pampas. Rainwater samples (n = 112) were collected throughout each rainfall in urban areas of the pampas having different degrees of land use and with extensive crop production plus subsurface-soil samples (n = 58) from the relevant periurban sites. The herbicides-analyzed by liquid-chromatography-mass-spectrometry-were detected in >80% of the rain samples at median-to-maximum concentrations of 1.24-67.3 µg·L-1 (GLP) and 0.22-26.9 µg·L-1(ATZ), while aminomethylphosphonic acid (AMPA) was detected at 34% (0.75-7.91 µg·L-1). In soils, GLP was more frequently registered (41%; 102-323 µg·kg-1) followed by ATZ (32%; 7-66 µg·kg-1) and then AMPA (22%; 223-732 µg·kg-1). The maximum GLP concentrations quantified in rainwater exceeded the previously reported levels for the USA and Canada. No associations were observed between soil and rainwater concentrations in the same monitoring areas-despite the soil's action as a source, as evidenced through the AMPA present in rainwater. Median GLP concentrations were significantly associated with isohyets, in an increasing gradient from the east to the west-as such in an inverse pattern to that of the annual rainfall volumes; whereas ATZ-rainwater levels exhibited no characteristic spatial configuration. The estimated annual deposition of GLP by rainfall indicated that more than onc source of a herbicide can lead to its presence in the atmosphere and points out the relevance of rainfall's contribution to the surface levels of a pollutant.

The effect of cypermethrin, chlorpyrifos, and glyphosate active ingredients and formulations on Daphnia magna (Straus).

Acute effects of active ingredients (a.i.) and formulations (F) of widely used pesticides were assessed by means of the Daphnia magna toxicity test. Studied pesticides were the insecticides, cypermethrin and chlorpyrifos, and the herbicide, glyphosate. Results were analyzed and compared according to statistical endpoints (LCx) and log-probit regressions of toxicity data. The potency of acute toxicity followed the order: chlorpyrifos F > chlorpyrifos a.i. > cypermethrin F > cypermethrin a.i. ≫ glyphosate F > glyphosate a.i. Three to five orders of magnitude differences between the toxicity (µg/L to mg/L) of insecticides and the herbicide were observed. A pairwise comparison between a.i. and F indicated that all formulations were more potent. Additionally, for the case of glyphosate, evidence suggests that the adjuvant contributes to formulation toxicity rather than to the enhancement of a.i. potency.

Influence of existing site contamination on sensitivity of Rhinella fernandezae (Anura, Bufonidae) tadpoles to Lorsban®48E formulation of chlorpyrifos.

Effects of the widely employed insecticide Lorsban(®)48E formulation of chlorpyrifos (CPF) was studied on Rhinella fernandezae tadpoles, a native species of Argentina, Brazil, Paraguay and Uruguay, under the hypothesis of a differential response of organisms from ponds of two sites with different degree of anthropogenic disturbance: S1 an unpolluted area, and S2 area with high degree of antropogenic disturbance. To collect a representative sample of the genotypic variability of each population, small portions from six clutches were taken randomly from each site when the period of clutching was finished. Embryos and tadpoles were maintained under controlled laboratory conditions. Toxicity tests were conducted under standardized conditions to study acute and chronic lethal (mortality) and sublethal effects (behavior, growth, and abnormalities), within the range of concentrations of 0.010 to 5 mg/L. Chronic effects were assessed with organisms from one of the demes (S1). CPF showed high toxicity on the tadpoles, inducing lethal and sublethal effects at 96 h exposure within a narrow range of concentrations from 0.066 to 0.887 mg/L. Results indicate that R. fernandezae tadpoles are below the 30th percentile in the species sensitivity distribution of existing data. The acute LC50, NOEC, and LOEC values were 0.151, 0.066, and 0.133 mg/L for S1, and 0.293, 0.177, and 0.266 mg/L for S2, respectively. Considering all acute end-points evaluated, the effects of CPF showed no significant differences (p = 0.3484) between the studied populations. CPF has more severe effects at higher concentrations than at higher times of exposure. Contaminants in S2 do not seem to induce local adaptation. Sublethal effects data and measured environmental concentrations indicate potential risk for populations inhabiting agroecosystems.

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications.

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.

Effects of pesticide formulations and active ingredients on the coelenterate Hydra attenuata (Pallas, 1766).

Lethal effects of active ingredients and formulations of widely used soybean pesticides were assessed with the Hydra attenuata toxicity test. Studied pesticides were insecticides chlorpyrifos and cypermethrin, and herbicide glyphosate. Results indicate the following toxicity trend: chlorpyrifos > cypermethrin > glyphosate. Tested active ingredients of insecticides and respective formulations did not significantly differ between them. Glyphosate formulation exhibited higher toxicity at low concentrations (LC(1-10)) respect to active ingredient, reversing this behavior at higher concentrations (LC(50-90)). Comparing H. attenuata sensitivity with existent toxicity data for aquatic organisms indicates that this species is poorly sensitive to tested insecticides and highly sensitive to the herbicide.