Honeybees as active samplers for microplastics

Microplastics are ubiquitous and their sampling is a difficult task. Honeybees interact with the environment inside their foraging range and take pollutants with them. In this work, we demonstrated for the first time that worker bees can act as active samplers of microplastics. We collected honeybees from apiaries located in the centre of Copenhagen and from nearby semiurban and rural areas. We showed the presence of microplastics in all sampled locations mostly in the form of fragments (52%) and fibres (38%) with average equivalent diameter of 64 ± 39 μm for fibres and 234 ± 156 μm for fragments. The highest load corresponded to urban apiaries, but comparable number of microplastics was found in hives from suburban and rural areas, which can be explained by the presence of urban settlements inside the foraging range of worker bees and to the easy dispersion of small microplastics by wind. Micro-FTIR analysis confirmed the presence of thirteen synthetic polymers, the most frequently of which was polyester followed by polyethylene and polyvinyl chloride. Our results demonstrated the presence of microplastics attached to the body of the honeybees and opens a new research pathway to their use as active biosamplers for anthropogenic pollutionThe authors acknowledge the financial support provided by the Spanish Government: CTM2016-74927-C2-1-R/2-R, and the Thematic Network of Micro- and Nanoplastics in the Environment (RED2018-102345-T, EnviroPlaNet Network). CE thanks the Spanish Ministry of Science, Innovation and Universities for the award of a pre-doctoral grant (FPI

Pesticide residues in food from Asia on the Norwegian market and the importance of efficient screening methods for pesticides

publishedVersio

First national survey of residues of active substances in honeybee apiaries across Spain between 2012 and 2016

11 Pág. Centro de Investigación en Sanidad Animal (CISA)This nationwide monitoring aimed to investigate the prevalence of residues of plant protection products (PPPs) and veterinary medicine products (VMPs) based on random selection of apiaries of Apis mellifera. For a three-year period (2012, 2013 and 2016), this study targeted 306 PPPs, VMPs and other active substances in 442 samples of bee bread honeycomb (BBHC) and 89 samples of honeybees collected from up to 177 apiaries. The results indicate that honeybees were most often exposed to residues of coumaphos, tau-fluvalinate, chlorfenvinphos, and acrinathrin, with a prevalence from a maximum of 98.8% to 49.4% in BBHC samples. Residues of coumaphos, tau-fluvalinate, amitraz (DMF + DMPF), carbendazim and orthophenylphenol were also frequently detected, from a maximum of 55.1% to 13.5% of the honeybee samples. Neonicotinoid residues, namely clothianidin and thiamethoxam, whose outdoor uses in crops are completely banned in EU, were not detected. Imidacloprid was found in 3.4% to 13.3% of samples during 2013 and 2016, respectively. Imidacloprid exceeded its acute toxicity (LD50) value for honey bees in two samples of BBHC. Fipronil was detected in 0.5% of the samples during 2013. The diversity of active substances found (% of different residues analyzed) ranged from 33.9% to 37.2% in BBHC from 2012, 2013 to 2016, and was of 26.5% in honeybees in 2016. In at least 54% of the samples, the total residue load was in the range of 200 to 1500 μg·kg-1. Up to 50% of BBHC samples were positive for one or two residues. No toxic residues for honeybees were detected in up to 88.8% of bee samples. This systematic surveillance of active substances assisted the evaluation of which target pesticides to look for and provided support to the competent authorities in the bee health decision-making.The authors acknowledge the voluntary participation of all the beekeepers involved in the program, the work carried out by the official veterinary services of all the participating Autonomous Communities and their bee inspectors in taking samples. Special mention to the work team of the Ministry of Agriculture, Fisheries and Food in the coordination of the surveillance program integrated by the General Subdirectorate of Animal Health and Hygiene and Traceability, the Department of Bee and Fish Diseases of the Central Veterinary Laboratory of Algete and the Agroalimentary Arbitration Laboratory of Aravaca.Peer reviewe

Life Cycle Assessment of biomass production in a Mediterranean greenhouse using different water sources: Groundwater, treated wastewater and desalinated seawater

An experimental biomass crop of Nicotiana tabacum was grown over a nine-month period inside a greenhouse situated in Almería, south-eastern Spain. Two irrigation methods corresponding to treated urban wastewater and groundwater, were arranged. No significant differences were observed in the total biomass produced on the treated wastewater and groundwater plots, which ranged from 17 to 28 kg m-2, depending on plant density. Environmental Life Cycle Assessment (LCA) was applied in order to gain knowledge of the potential impacts of using either treated wastewater, groundwater, or desalinated water for irrigation. The LCA study included all the processes involved in agricultural production up to the final plant cutting. Since desalinated water was not actually used in the experiment, the experimental data from tobacco irrigated with groundwater was used in the LCA. Impact categories included were: global warming; acidification; water eutrophication; primary energy use; as well as aquatic and terrestrial ecotoxicity. Special attention was put on the ecotoxicity of emerging and priority pollutants in treated wastewater, as well as on soil quality impacts, namely soil organic carbon deficit and soil salinisation. The results show that using desalinated water leads to higher environmental impacts in several impact categories, including global warming, energy use, soil quality, and aquatic ecotoxicity. As an example, primary energy use increases by 80% and 50% as compared to using treated wastewater and groundwater, respectively. On the other hand, wastewater pollutants in irrigation water may involve a relevant contribution to terrestrial ecotoxicity. For this reason, the impact score of the wastewater-irrigated crop is 23% and 35% higher as compared to the crop using desalinated water and groundwater, respectively.Intensive agriculture Life Cycle Assessment (LCA) Ecotoxicity Soil impacts Reclaimed water Desalination

Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography–tandem mass spectrometry analysis in hospital effluent wastewaters

10 pages, 3 figures, 3 tables.-- PMID: 16546199 [PubMed].-- Printed version published May 12, 2006.-- Issue title: ExTech 2005 - 7th International Symposium on Advances in Extraction Technologies (Campinas, Brazil, Nov 13-15, 2005).Presented at the 1st International Workshop on Liquid Chromatography–Tandem Mass Spectrometry for Screening and Trace Level Quantitation in Environmental and Food Samples, Barcelona, Spain, 20–21 June 2005.A multi-residue analytical method has been developed and validated for determining a selection of 16 pharmaceuticals: the anti-epileptic carbamazepine, seven analgesic/anti-inflammatory drugs (mefenamic acid, indomethacine, ibuprofen, naproxen, diclofenac, ketorolac and acetaminophen), the analgesic opiate codeine, two antidepressants (fluoxetine and paroxetine), β-blockers (atenolol and propranolol), antibiotic (trimethoprim, metronidazole, and erythromycin) and the anti-ulcer ranitidine in hospital effluent wastewaters. The method allows simultaneous extraction of the pharmaceuticals compounds by solid-phase extraction (SPE) using the Waters Oasis HLB at pH 7. The analytes were then identified and quantitatively determined by liquid chromatography–tandem mass spectrometry (LC–MS–MS) using multiple reaction monitoring (MRM). Recoveries of the pharmaceuticals were higher than 75%, with the exception of ranitidine (45%) and the overall variability of the method was below 9%. The instrumental detection limit (IDL) varied between 2 and 31 pg injected, the method detection limit (LOD) was between 7 and 47 ng/L in spiked hospital effluent. The precision of the method, calculated as relative standard deviation (RSD), ranged from 0.3 to 4.9%. A detail study off matrix effect is included in this work, regarding to signal suppression in these effluent wastewaters from a hospital complex samples. The developed analytical method was applied for preliminary data results in effluent wastewaters from a hospital.This study was financially supported by the European Union EMCO project [INCO-CT-2004-509188], by the Spanish Ministerio de Educación y Ciencia Project EVITA (CTM2004-06255-CO3) and by the Spanish Ministry of Science and Technology (PPQ2002-04573-C04-03). M. Gómez acknowledges the fellowship from the Spanish Ministry of Science and Technology. Waters (Milford, USA) is gratefully acknowledged for providing the SPE cartridges and Merck (Darmstadt, Germany) for providing the HPLC columns. The authors also wish to thank R. Chaler and D. Fanjul for their kind support with the LC–MS–MS experiments.Peer reviewe

Analysis by liquid chromatography-electrospray ionization tandem mass spectrometry and acute toxicity evaluation for beta-blockers and lipid-regulating agents in wastewater samples

8 pages, 2 figures, 3 tables.-- PMID: 15387181 [PubMed].-- Printed version published Aug 13, 2004.-- Presented at the 3rd Meeting of the Spanish Association of Chromatography and Related Techniques and the European Workshop: 3rd Waste Water Cluster, Aguadulce (Almeria), Spain, Nov 19–21, 2003.This paper describes a multiresidue method for the extraction and determination of two therapeutic groups of pharmaceuticals, lipid-regulating agents (clofibric acid, bezafibrate, gemfibrocil, fenofibrate) and β-blockers (atenolol, sotalol, metoprolol, betaxolol) in waters by solid-phase extraction followed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC–ESI-MS–MS). Recoveries obtained from spiked HPLC water, as well as, from spiked real samples (sewage treatment plants influent and effluents, river and tap water) were all above 60%, with the exception of betaxolol with a 52% recovery. The quantitative MS analysis was performed using a multiple reaction monitoring. The LC–MS–MS method gave detection limits ranging from 0.017 to 1.25 μg/l in spiked effluent. Precision of the method, calculated as relative standard deviation, ranged from 3.7 to 18.5%. Individual and combined effects on Daphnia magna were evaluated for both therapeutic groups. Individual effects in culture medium showed these compounds as not harmful and not toxic, an exception is fenofibrate that was found to be harmful, but at high, in the environment unrealistic concentrations (EC50 of 50 mg/l). Combined effect in wastewater showed synergistic toxic effects at low concentration level (2 μg/l).This study was financially supported by the European Commission Project (P-THREE No. EVK1-CT2002-0116) and the Spanish Ministerio de Ciencia y Tecnologia (PPQ2002-10945-E and PPQ2001-1805-CO3-01).Peer reviewe

Determination of photodegradation and ozonation by products of linear alkylbenzene sulfonates by liquid chromatography and ion chromatography under controlled laboratory experiments

11 pages, 6 figures, 4 tables.-- PMID: 18969570 [PubMed].-- Printed version published Sep 8, 2004.-- Issue title: "Southern and Eastern Africa Network for Analytical Chemists".A Suntest solar simulator with arc xenon lamp was used to irradiate pure linear alkylbenzene sulfonates (LAS) standard and some commercial LAS solutions. The ozonation treatment was carried out in a pilot plant air-lift type reactor. Kinetic degradation curves were obtained showing an apparent first order reaction in both cases. Extraction and preconcentration of samples was carried out by off-line SPE using polymeric an RP-18 cartridges with recoveries varying from 77 to 93% for the LAS compounds. For LC chromatographic elution of LAS and degradation products an ion pair based on 5 mM triethylamine and 5 nM acetic acid had to the acetonitrile–water or methanol–water mobile phases. Fluorescence detection was achieved at 225 and 295 nm as excitation and emission radiation wavelength, respectively. Degradation by products were identified by liquid chromatography electrospray mass spectrometry detection (LC–ESI-MS). Ion chromatography (IC) was used to analyze refractory species such as oxalate, formate and acetate ions which were present in the treated solution even after 3 h of ozone treatment. The LAS mixture was almost totally degraded in less than 20 min using O3/H2O2, the reaction being faster than in the case of catalyzed photodecomposition. TOC removal reached 84% after 3 h of ozonation process.This work has been supported by the Project FEDER (IF-AMB98-08). J. Fernandez would also like to acknowledge the support from Universidad de Caldas in Colombia and to thank the Convenio Andres Bello for economic support.Peer reviewe

Pilot survey monitoring pharmaceuticals and related compounds in a sewage treatment plant located on the Mediterranean coast

10 pages, 3 figures, 3 tables.-- PMID: 16962638 [PubMed].-- Available online on Sep 14, 2007.A one-year monitoring study was performed to evaluate the occurrence, persistence and fate of a group of 14 organic compounds in a sewage treatment plant (STP) located in the south of Spain. These results are part of a more extensive study, financed by the Spanish Ministry of Research with the aim to evaluate the traceability of new pollutants on the Mediterranean coast and to determine the removal efficiency of sewage treatment plants (STP) for these pollutants. The compounds which have been analyzed include pharmaceuticals of various therapeutic categories (ibuprofen, acetaminophen, dipyrone, diclofenac, carbamazepine and codeine), pesticides (chlorfenvinfos and permethrin), caffeine, triclosan, bisphenol A and three of their more relevant metabolites (1,7-dimethylxanthine, carbamazepine 10,11-epoxide and 2,7/2,8-dichlorodibenzo-p-dioxin). An SPE/GC–MS multi-residue analytical method was developed and validated to facilitate simultaneous determination of these compounds in both influent and effluent wastewater. The method provided mean recoveries higher than 75%, with the exception of 2,7/2,8-dichlorodibenzo-p-dioxin, dipyrone and permethrin which exhibited recoveries lower than 22%. The overall variability of the method was below 14%. The method detection limit (LOD) was between 1 and 100 ng l 1 and precision, which was calculated as relative standard deviation (RSD), ranged from 1.8% to 11.2%. The application of the proposed method has allowed the identification of all the target compounds at mean concentrations which ranged from 0.12 to 134 μg l-1 in the influent and from 0.09 to 18.0 μg l-1 in the effluent. The removal efficiencies of the STP for these compounds varied from 20% (carbamazepine) to 99% (acetaminophen), but in all cases resulted insufficient in order to avoid their presence in treated water and subsequently in the environment.The authors wish to thank the Spanish Ministry of Education and Science (Projects No PPQ2001-1805-C03-03 and PPQ2002-04573-C04-03) for financial support.Peer reviewe