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The occurrence of pharmaceuticals in surface water has been barely studied in Latin America. This work aimed to i) develop a multi-residue liquid chromatography- triple quadrupole mass spectrometry (LC–MS/MS) method for the determination of pharmaceutical active compounds (PhACs); ii) monitor 70 PhACs in three urban-influenced rivers in San José, Costa Rica; and iii) perform the risk assessment of detected compounds and ecotoxicological evaluation on water samples. Caffeine, 1,7-dimethylxanthine, naproxen, gemfibrozil and ibuprofen were the most frequent among 23 detected compounds. Concentrations ranged from 0.013 μg/L to 53.8 μg/L (62 % detections between 0.1 μg/L–1 μg/L), and the highest values corresponded to caffeine, 1,7-dimethylxanthine, ofloxacin, gemfibrozil and cephalexin. The environmental risk estimated using the hazard quotient (HQ) approach, revealed four and eleven compounds with medium and high risk, respectively. The highest risk (HQ >10) was determined for diphenhydramine, risperidone, fluoxetine, trimethoprim, ofloxacin and azithromycin; nonetheless, high risk (HQ >1) was also estimated for caffeine, diclofenac, clarithromycin, gemfibrozil and ibuprofen. Total HQ sample values (ΣHQ), calculated as the sum of individual HQs for each detected compound, revealed the highest hazard in surface water near wastewater treatment plant discharges, followed by the locations of higher urban influence (in the Virilla river). Ecotoxicological evaluation showed no acute toxicity towards Daphnia magna and Vibrio fischeri in surface water samples; on the contrary, toxicity towards Lactuca sativa (germination tests) showed a similar pattern to that determined with the ΣHQ, although the highest toxicity was observed downstream with respect to the urban influence of the metropolitan area. These findings help to visualize the importance of pharmaceutical residues in the overall toxicity of surface water samples, and remark the relevance of monitoring these compounds, as an input for the implementation of future mitigation actions. Universidad de Costa Rica/[802-B7-A09]/UCR/Costa Rica Universidad de Costa Rica/[802-B8-510]/UCR/Costa Rica Universidad de Costa Rica/[802-B8-144]/UCR/Costa Rica Universidad de Costa Rica/[802-B8-145]/UCR/Costa Rica Ministerio de Ciencia, Tecnología y Telecomunicaciones/[FI-197B-17]/MICITT/Costa Rica Ministerio de Ciencia, Tecnología y Telecomunicaciones/[FI-056B-17]/MICITT/Costa Rica UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro en Investigación en Contaminación Ambiental (CICA) UCR::Vicerrectoría de Docencia::Salud::Facultad de Microbiología

Many small parasitoid wasps have a black-orange-black (BOB) color pattern, which is usually present in both sexes. A likely function of this widespread pattern is aposematic (warning) coloration, but this has never been investigated. To test this hypothesis, we presented spider predators(Lyssomanes jemineus), both field-captured and lab-reared individuals, to a species with the BOB pattern and a congeneric all-black species in each of four scelionid genera (Baryconus, Chromoteleia, MacroteleiaandScelio). Each spider/wasp trial was filmed for 40 minutes under controlled conditions and three behavioral responses (detect, attack, avoid) were recorded in each of 136 trials, never using the same predator and prey more than once. In order to better understand the results obtained, two additional studies were performed. First, the reflection spectrum of the cuticle of the wasp and a theoretical visual sensibility model of the spider were used to calculate a parameter we called “absorption contrast” that allowed us to compare the perception contrast between black and orange in each wasp genus as viewed by the spider. Second, acute toxicity trials with the water flea,Daphnia magna, were performed to determine toxicity differences between BOB and non-BOB wasps. By combining the results from the three types of experiments, together with a statistical analysis, we confirmed that BOB color pattern plays an aposematic role.

The presence of pharmaceuticals in the environment is known to have multiple origins; livestock activities comprise one scarcely studied source, both globally and specially in Latin-America. This work aims to study the occurrence of pharmaceuticals in wastewater from swine farms and their surrounding surface waters, in a highland livestock production area of Costa Rica. The monitoring of 70 pharmaceutical active compounds resulted in the detection of 10 molecules in farm wastewater (influents and effluents of the on-farm treatment system), including compounds of animal and human use. A 57% of effluents showed high hazard (ΣHQ > 1), mainly due to the compounds risperidone, ketoprofen, ibuprofen and naproxen. Additionally, ecotoxicological tests with Daphnia magna and Microtox classified at least 21% of the effluents as very toxic (10 < TU ≤ 100); likewise, 86% of effluents exhibited germination index (GI) inhibition values over 90% for Lactuca sativa. Seven molecules were detected in surface water, six of them of human use (1,7-dimethylxanthine, caffeine, cephalexin, carbamazepine, gemfibrozil, ibuprofen) and one (acetaminophen) of dual (human and veterinary) use; nonetheless, most of the detections were found in sampling points closer to human settlements than animal farms. Considering the set of molecules and their distribution, the livestock influence on surface water seems minimal in comparison with the urban influence. Only 16% of surface water samples showed high risk, mainly due to ibuprofen, gemfibrozil and caffeine; similarly, 45% samples presented GI inhibition >20% (no toxicity was determined towards Daphnia magna or Microtox). These findings in surface water suggest an incipient environmental risk in the area. Universidad de Costa Rica/[802-B7-A09]/UCR/Costa Rica Universidad de Costa Rica/[802-B8-510]/UCR/Costa Rica Universidad de Costa Rica/[802-B8-144]/UCR/Costa Rica Universidad de Costa Rica/[802-B8-145]/UCR/Costa Rica Ministerio de Ciencia, Tecnología y Telecomunicaciones/[FI-197B-17]/MICITT/Costa Rica Ministerio de Ciencia, Tecnología y Telecomunicaciones/[FI-056B-17]/MICITT/Costa Rica UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro en Investigación en Contaminación Ambiental (CICA)

The continuous release of pharmaceuticals from WWTP effluents to freshwater is a matter of concern, due to their potential effects on non-target organisms. The occurrence of pharmaceuticals in WWTPs and their associated hazard have been scarcely studied in Latin American countries. This study aimed at monitoring for the first time the occurrence of 70 pharmaceutical active compounds (PhACs) in WWTPs across Costa Rica; the application of the hazard quotient (HQ) approach coupled to ecotoxicological determinations permitted to identify the hazard posed by specific pharmaceuticals and toxicity of the effluents, respectively. Thirty-three PhACs were found, with 1,7-dimethylxanthine, caffeine, acetaminophen, ibuprofen, naproxen, ketoprofen and gemfibrozil being the most frequently detected (influents/effluents). HQ for specific pharmaceuticals revealed 24 compounds with high/medium hazard in influents, while the amount only decreased to 21 in effluents. The top HQ values were obtained for risperidone, lovastatin, diphenhydramine and fluoxetine (influent/effluent samples), plus caffeine (influent) and trimethoprim (effluent). Likewise, the estimation of overall hazard in WWTP samples (sum of individual HQ, ∑HQ) demonstrated that every influent and 96% of the effluents presented high hazard towards aquatic organisms. Ecotoxicological analysis (Daphnia magna, Lactuca sativa and Microtox test) revealed that 16.7% of the effluents presented toxicity towards all benchmark organisms; the phytotoxicity was particularly frequent, as inhibition values ≥20% in the germination index for L. sativa were obtained for all the effluents. The ∑HQ approach estimated the highest hazard in urban wastewater, while the ecotoxicological results showed the highest toxicity in hospital and landfill wastewater. Likewise, ecotoxicological results and ∑HQ values showed a rather poor correlation; instead, better correlations were obtained between ecotoxicological parameters and HQ values for some individual pharmaceuticals such as cephalexin and diphenhydramine. Findings from this study provide novel information on the occurrence of pharmaceuticals and the performance of WWTPs in the tropical region of Central America. UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro en Investigación en Contaminación Ambiental (CICA) UCR::Vicerrectoría de Docencia::Salud::Facultad de Microbiología UCR::Sedes Regionales::Sede del Caribe