Angelina Pena

Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment

Pharmaceuticals are biologically active and persistent substances which have been recognized as a continuing threat to environmental stability. Chronic ecotoxicity data as well as information on the current distribution levels in different environmental compartments continue to be sparse and are focused on those therapeutic classes that are more frequently prescribed and consumed. Nevertheless, they indicate the negative impact that these chemical contaminants may have on living organisms, ecosystems and ultimately, public health. This article reviews the different contamination sources as well as fate and both acute and chronic effects on non-target organisms. An extensive review of existing data in the form of tables, encompassing many therapeutic classes is presented.

A review on ochratoxin A occurrence and effects of processing of cereal and cereal derived food products.

Ochratoxin A (OTA) continues to grab global attention and concern for the hazard and impact that embody for both human and animals, based on its toxicity and occurrence. Despite OTA has been described in a myriad of foodstuffs, cereal and its derivatives remain the major contributors to OTA exposure. For that reason, a critical review on OTA occurrence reported by recent studies worldwide focusing on unprocessed and processed cereal foodstuffs is made in this work. Special attention is drawn to the major cereal derived products, namely flour, bread, breakfast cereals, baby/infant foods and the inherently involved technological food processing methods and its influence on the redistribution and chemical modification of OTA. The paper further examines the factors that influence the OTA content of cereal and its derived products, explicitly the different ecological niches of the ochratoxigenic mycobiota -Aspergillus spp. and Penicillium verrucosum, the agricultural practice involved, harvest procedures and storage conditions, the type of grain, and the nature and extent of technological processing as well as the ultimate stages of analytical quality level of the sampling and analysis of the suspected ingredients or foods.

Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: identification of ecologically relevant pharmaceuticals.

The impact of effluent wastewaters from four different hospitals: a university (1456 beds), a general (350 beds), a pediatric (110 beds) and a maternity hospital (96 beds), which are conveyed to the same wastewater treatment plant (WWTP), was evaluated in the receiving urban wastewaters. The occurrence of 78 pharmaceuticals belonging to several therapeutic classes was assessed in hospital effluents and WWTP wastewaters (influent and effluent) as well as the contribution of each hospital in WWTP influent in terms of pharmaceutical load. Results indicate that pharmaceuticals are widespread pollutants in both hospital and urban wastewaters. The contribution of hospitals to the input of pharmaceuticals in urban wastewaters widely varies, according to their dimension. The estimated total mass loadings were 306 g d(-1) for the university hospital, 155 g d(-1) for the general one, 14 g d(-1) for the pediatric hospital and 1.5 g d(-1) for the maternity hospital, showing that the biggest hospitals have a greater contribution to the total mass load of pharmaceuticals. Furthermore, analysis of individual contributions of each therapeutic group showed that NSAIDs, analgesics and antibiotics are among the groups with the highest inputs. Removal efficiency can go from over 90% for pharmaceuticals like acetaminophen and ibuprofen to not removal for β-blockers and salbutamol. Total mass load of pharmaceuticals into receiving surface waters was estimated between 5 and 14 g/d/1000 inhabitants. Finally, the environmental risk posed by pharmaceuticals detected in hospital and WWTP effluents was assessed by means of hazard quotients toward different trophic levels (algae, daphnids and fish). Several pharmaceuticals present in the different matrices were identified as potentially hazardous to aquatic organisms, showing that especial attention should be paid to antibiotics such as ciprofloxacin, ofloxacin, sulfamethoxazole, azithromycin and clarithromycin, since their hazard quotients in WWTP effluent revealed that they could pose an ecotoxicological risk to algae.

An overview of analytical methodologies for the determination of antibiotics in environmental waters

The widespread occurrence of antibiotics as contaminants in the aquatic environment has increased attention in the last years. The concern over the release of antibiotics into the environment is related primarily to the potential for the development of antimicrobial resistance among microorganisms. This article presents an overview of analytical methodologies for the determination of quinolone (Qs) and fluoroquinolone (FQs), macrolide (MLs), tetracycline (TCs), sulfonamide (SAs) antibiotics and trimethoprim (TMP) in different environmental waters. The analysis of these antibiotics has usually been carried out by high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) and to a lesser extent by ultraviolet (UV) or fluorescence detection (FD). A very important step before LC analysis is sample preparation and extraction leading to elimination of interferences and prevention of matrix effect and preconcentration of target analytes.

Human ochratoxin a biomarkers--from exposure to effect.

Ochratoxin A (OTA) is a nephrotoxic mycotoxin that has received particular attention because of the toxic effects, widespread occurrence in contaminated food and feed chain, suspected causal effect on nephropathies, and, more recently, possibility of exposure by inhalation in domicile and occupational settings. Biomarkers have been used not only to ascertain the role of OTA in inducing chronic renal failure diseases, but also as a means to portray general populations’ risk to the mycotoxin. Biomonitoring can thus be used to assess internal OTA exposure, with no need to recognize the main source of exposure. And so it presents undeniable advantages over the monitoring of external dose. With a just right understanding of biomarkers, it is possible to follow the trail from exposure right to effect, and so contribute both to surveillance plans and etiological studies. In recognition of the long serum half-life and the renal elimination of OTA, most of the studies present serum/plasma and/or urine analyses as markers of exposure. In this review and for each of these main matrices, a comparison over the advantages and disadvantages is offered. Although currently limited, an overview of the current knowledge on OTA biomarkers and the influential role of the individual characteristics, namely gender and age, along with season and geographical location is given. Attention is also given to the ongoing debate over the existence of OTA-DNA adducts, a biomarker of effective dose regarded as an alternative to biomarkers of internal dose. Although unspecific, OTA effect biomarkers are also reviewed.

Environmental impact of pharmaceuticals from Portuguese wastewaters: geographical and seasonal occurrence, removal and risk assessment

The occurrence, fate, geographical and seasonal influence and environmental risk assessment of eleven of the most consumed pharmaceuticals in Portugal were studied in wastewater treatment plants (WWTPs) influents and (WWI) and effluents (WWE). WWI and WWE samples, from two sampling campaigns (spring and summer), in 2013, were evaluated in 15 different WWTPs across the country, by solid phase extraction (SPE) and liquid chromatography coupled with tandem mass detection (LC-MS-MS). Lipid regulators were the most frequently found in WWI and WWE (184.1 and 22.3mg/day/1000 inhab., respectively), followed by anti-inflammatories (1339.4 and 15.0mg/day/1000 inhab., respectively), and antibiotics (330.7 and 68.6 mg/day/1000 inhab., respectively). Anxiolytics were the least detected with 3.3 and 3.4 mg/day/1000 inhab. in WWI and WWE, respectively. The mass loads, both in WWI and WWE, were higher in summer than those found during the spring season, being remarkable the high values registered in a region where population triplicates in this time of the year. The mean removal efficiency achieved was of 94.5%, nonetheless, between the different therapeutic groups, as well as within each group, important variations in removal were observed, going from not eliminated to 100%. In the summer higher efficiencies were observed regarding lipid regulators and antibiotics. Furthermore, an important outcome was the evaluation, by means of risk quotients (RQs), of the potential ecotoxicological risk posed by the selected pharmaceuticals to different aquatic organisms, exposed to the effluents studied. Ciprofloxacin, bezafibrate, gemfibrozil, simvastatin and diclofenac showed RQs higher than one, being expected that these pharmaceuticals might pose a threat to the three trophic levels (algae, daphnids and fish) evaluated. These results highlight the importance of these monitoring studies, as required by the Directive 2013/39/EU, in order to minimize their aquatic environmental contamination and support future prioritization measures.

Mycotoxin food and feed regulation and the specific case of ochratoxin A: a review of the worldwide status

Mycotoxins are naturally occurring contaminants whose presence in food- and feedstuffs cannot be completely avoided. The safety and economic impact arising from the commercialization of mycotoxin-contaminated food and feed supply chain is considerable and acknowledged. To protect consumers from mycotoxin-derived health risks, many countries have adopted regulations or guidelines to limit exposure. Similar to regulation for other mycotoxins, the regulatory status of ochratoxin A (OTA) lacks consensus. Although this was one of the first fungal toxins to be subjected to compliance control due to its toxic properties, the conflict between the prime objective of consumer health safeguard and the economic interests of producers and traders remains. One of the key challenges facing policymakers is to balance these conflicting demands and reach consensual regulatory actions or limits. The noteworthy transboundary implications are recognized, both in the case of absence as the unsubstantiated tightening of regulatory limits. This paper scrutinizes the rationales and implications of mycotoxin regulation, with special attention devoted to OTA. In view of the ongoing debate concerning this complex issue, a review of the arguments and suggested strategies proposed by different parties is also made. The specific case of OTA regulation in food and feed is updated and analysed at a European Union and global level.

Occurrence of fumonisins B1 and B2 in Portuguese maize and maize-based foods intended for human consumption.

Fumonisin B1 (FB1) and fumonisin B2 (FB2) are mycotoxins mainly produced by Fusarium verticillioides and Fusarium proliferatum, which are field pathogens of maize. A survey was conducted on the incidences of FB1 and FB2 in both maize and derived products purchased in Portugal. The analytical method involved extraction with methanol–water, clean-up by immunoaffinity column and derivatization with naphthalene-2,3-dicarboxaldehyde. Determination was carried out by high-performance liquid chromatography (HPLC) with spectrofluorimetric detection, with liquid chromatography/mass spectrometry (LC/MS) confirmation. The presence of FB1 and FB2 was determined in 67 samples of maize and maize-based foods, such as flour, semolina, starch, sweet maize, cornflakes and other breakfast cereals, and snacks collected in 2005. FBs were found in 15 samples at concentrations ranging from 113 to 2026 µg kg−1. Two of the samples showed higher contamination levels than the limits established by the European Commission Regulation. None of the samples contained levels of fumonisins that would lead to an exposure exceeding the tolerable daily intake (TDI).

Ochratoxin A in feed of food-producing animals: An undesirable mycotoxin with health and performance effects

Mycotoxins are secondary fungal metabolites, whose presence in feed- and foodstuffs is unavoidable. Ochratoxin A (OTA) is one of the known mycotoxins with greatest public health and agro-economic significance. Several toxic effects have been ascribed following exposure, namely nephrotoxicity, as well negative impacts in the performance of farm animals, resulting in major economic implications. Of no less importance for the route of human exposure that can also embody the carry-over of OTA from feed into animal-derived products is also a concern. For all these reasons the present article updates the worldwide occurrence of OTA in different raw ingredients and finished feed destined to food-producing animals. After that a brief characterization of specie susceptibility and the major rationales is made. An historical overview of field outbreaks linked to OTA exposure in farm animals, concerning the implicated feeds, contamination levels and major clinical and productivity effects is presented. Finally a review of the major animal health and performance potential impacts of animals being reared on contaminated feed is made allied to a perspective regarding its co-occurrence with other mycotoxins, and simultaneous parasitic and bacterial infections. Ultimately, this article aims to be instructive and draw attention to a mycotoxin so often neglected and elapsed from the list of differential diagnosis in farm practice. For the unpredictability and unavoidability of occurrence, OTA will definitely be an enduring problem in animal production.

Reviewing the serotonin reuptake inhibitors (SSRIs) footprint in the aquatic biota: Uptake, bioaccumulation and ecotoxicology

Selective serotonin re-uptake inhibitors (SSRIs) antidepressants are amongst the most prescribed pharmaceutical active substances throughout the world. Their presence, already described in different environmental compartments such as wastewaters, surface, ground and drinking waters, and sediments, and their remarkable effects on non-target organisms justify the growing concern about these emerging environmental pollutants. A comprehensive review of the literature data with focus on their footprint in the aquatic biota, namely their uptake, bioaccumulation and both acute and chronic ecotoxicology is presented. Long-term multigenerational exposure studies, at environmental relevant concentrations and in mixtures of related compounds, such as oestrogenic endocrine disruptors, continue to be sparse and are imperative to better know their environmental impact.