Pedro N. Carvalho

A review of plant–pharmaceutical interactions: from uptake and effects in crop plants to phytoremediation in constructed wetlands

Pharmaceuticals are commonly found both in the aquatic and the agricultural environments as a consequence of the human activities and associated discharge of wastewater effluents to the environment. The utilization of treated effluent for crop irrigation, along with land application of manure and biosolids, accelerates the introduction of these compounds into arable lands and crops. Despite the low concentrations of pharmaceuticals usually found, the continuous introduction into the environment from different pathways makes them ‘pseudo-persistent’. Several reviews have been published regarding the potential impact of veterinary and human pharmaceuticals on arable land. However, plant uptake as well as phytotoxicity data are scarcely studied. Simultaneously, phytoremediation as a tool for pharmaceutical removal from soils, sediments and water is starting to be researched, with promising results. This review gives an in-depth overview of the phytotoxicity of pharmaceuticals, their uptake and their removal by plants. The aim of the current work was to map the present knowledge concerning pharmaceutical interactions with plants in terms of uptake and the use of plant-based systems for phytoremediation purposes.

Potential of Phragmites australis for the removal of veterinary pharmaceuticals from aquatic media

The potential of Phragmites australis was evaluated for the removal of three veterinary drugs, enrofloxacin (ENR), ceftiofur (CEF) and tetracycline (TET), from aquatic mediums. Results showed that the plant promoted the removal of 94% and 75% of ENR and TET, respectively, from wastewater. Microbial abundance estimation revealed that microorganisms were not a major participant. Occurrence of drugs adsorption to plant roots was observed in small extension. Therefore, main mechanisms occurring were drug removal by plant uptake and/or degradation. Present results demonstrated the potential of P. australis-planted beds to be used for removal of pharmaceuticals from livestock and slaughterhouse industries wastewater.

Sanitation in constructed wetlands: A review on the removal of human pathogens and fecal indicators

Removal of human pathogens from wastewater is a critical factor with linkage to human health. Constructed Wetlands (CWs) are environmental friendly ecosystems that are applicable not only for chemical pollution control, but also for the reduction of pathogens from wastewater. Yet the knowledge on the fate and removal of such indicator bacteria in CWs is still not sufficient due to the complexity of removal mechanisms and influencing factors. This review serves to provide a better understanding of this state-of-the-art technology, which is necessary for further investigations and design development. The fecal indicator bacteria in CWs mainly come from three sources, namely, influent wastewaters, regrowth within the CWs, and animal activities. The properties of microbial contamination vary depending on the different sources. The removal of pathogens is a complex process that is influenced by operational parameters such as hydraulic regime and retention time, vegetation, seasonal fluctuation, and water composition. The most frequent and well-validated removal mechanisms include natural die-off due to starvation or predation, sedimentation and filtration, and adsorption. The concentration of the main fecal indicator bacteria in the effluent was found to be exponentially related to the loading rate. Generally, horizontal subsurface flow CWs have better reduction capacity than free water surface flow CWs, and hybrid wetland systems were found to be the most efficient due to a longer retention time. Further improvement of fecal indicator bacteria removal in CWs is needed, however, levels in CW effluents are still higher than most of the regulation standards for reuse.

Potential of constructed wetlands microcosms for the removal of veterinary pharmaceuticals from livestock wastewater

The aim of the present work was to evaluate, at microcosm level, the capacity of constructed wetlands (CWs) to remove veterinary pharmaceutical compounds, from wastewater. Results indicated that CWs have potential to mitigate the release of veterinary drugs, namely enrofloxacin (ENR, a fluoroquinolone) and tetracycline (TET, tetracyclines family). Removal efficiencies of 94% and 98% where achieved for TET and ENR, respectively, when treating pigfarm wastewater effluent doped at 100 μg L(-1) drug level, along twelve weeks. Occurrence of adsorption of the drugs to CWs substrate may be the predominant mechanism for ENR, although for TET there are signs that degradation is also occurring.

Microbial community dynamics associated with veterinary antibiotics removal in constructed wetlands microcosms

This study aimed to evaluate the response of the microbial community from CWs microcosms tested for the removal of two veterinary antibiotics, enrofloxacin (ENR) and tetracycline (TET), from livestock industry wastewater. Three treatments were tested (control, ENR or TET (100 μg L(-1))) over 12 weeks in microcosms unplanted and planted with Phragmites australis. CWs removal efficiency was relatively stable along time, with removals higher than 98% for ENR and 94% for TET. In addition, CWs were able to reduce wastewater toxicity, independently of antibiotics presence. Despite no significant differences were observed in terms of microbial abundance, bacterial richness or diversity, analysis of similarities (two-way crossed ANOSIM) showed a significant effect of both time and treatments in bacterial community structure. This study points to CWs applicability for veterinary antibiotics removal from livestock wastewaters, showing that CWs microbial communities were able to adapt without significant changes in their diversity or depuration capacity.

Phytoremediation of imazalil and tebuconazole by four emergent wetland plant species in hydroponic medium.

Pollution from pesticide residues in aquatic environments is of increasing concern. Imazalil and tebuconazole, two commonly used systemic pesticides, are water contaminants that can be removed by constructed wetlands. However, the phytoremediation capability of emergent wetland plants for imazalil and tebuconazole, especially the removal mechanisms involved, is poorly understood. This study compared the removal of both pesticides by four commonly used wetland plants, Typha latifolia, Phragmites australis, Iris pseudacorus and Juncus effusus, and aimed to understand the removal mechanisms involved. The plants were individually exposed to an initial concentration of 10 mg/L in hydroponic solution. At the end of the 24-day study period, the tebuconazole removal efficiencies were relatively lower (25%-41%) than those for imazalil (46%-96%) for all plant species studied. The removal of imazalil and tebuconazole fit a first-order kinetics model, with the exception of tebuconazole removal in solutions with I. pseudacorus. Changes in the enantiomeric fraction for imazalil and tebuconazole were detected in plant tissue but not in the hydroponic solutions; thus, the translocation and degradation processes were enantioselective in the plants. At the end of the study period, the accumulation of imazalil and tebuconazole in plant tissue was relatively low and constituted 2.8-14.4% of the total spiked pesticide in each vessel. Therefore, the studied plants were able to not only take up the pesticides but also metabolise them.

Simultaneous determination of several veterinary pharmaceuticals in effluents from urban, livestock and slaughterhouse wastewater treatment plants using a simple chromatographic method

Minocycline, oxytetracycline, tetracycline, enrofloxacin and ceftiofur, commonly used veterinary pharmaceuticals, were searched in four urban, two livestock and two slaughterhouse effluents from wastewater treatment plants (WWTPs) in the north of Portugal. A simple method that includes solid-phase extraction followed with analysis by high-performance liquid chromatography with diode array detector was established and applied to the simultaneous determination of the five pharmaceuticals in WWTP effluents. This method, which is expeditious, inexpensive and available in most laboratories, showed to be useful for screening for problematic levels of drugs in WWTP effluents. It is known that several livestock and slaughterhouse effluents (pre-treated or treated) are discharged to the urban network before discharge into the environment. The presence of these drugs in such effluents can constitute a significant environmental problem that should be addressed, by the monitoring of these drugs and by implementation of methodologies that contribute to their decrease/elimination from wastewaters. Minocycline (≤6 μg L(-1)), oxytetracycline (≤7 μg L(-1)), tetracycline (≤6 μg L(-1)) and enrofloxacin (<2 μg L(-1)) could be detected and/or quantified in three urban effluents. Detectable levels of enrofloxacin (<2 μg L(-1)) and quantifiable levels of tetracycline (≤15 μg L(-1)) were found in the slaughterhouse effluents.

Dietary patterns and asthma prevalence, incidence and control

The increased asthma prevalence in westernized societies has been suggested to be related to environment exposures and lifestyle changes, particularly diet. We aimed to explore the association between dietary patterns and asthma prevalence, incidence and control in a nationally representative population.

Functionality of microbial communities in constructed wetlands used for pesticide remediation: Influence of system design and sampling strategy

The objective of this study was to compare the microbial community metabolic function from both unsaturated and saturated constructed wetland mesocosms (CWs) when treating the pesticide tebuconazole. The comparison was performed for both interstitial water and substrate biofilm by community level physiological profiling (CLPP) via BIOLOG™ EcoPlates. For each CW design (saturated or unsaturated), six mesocosms were established including one unplanted and five planted individually with either Juncus effusus, Typha latifolia, Berula erecta, Phragmites australis or Iris pseudacorus. Microbial activity and metabolic richness of interstitial water from unsaturated CWs were significantly lower than that from saturated CWs. However, in general, the opposite result was observed for biofilm samples. Wetland plants promoted significantly higher biofilm microbial activity and metabolic richness than unplanted CWs in both CW designs. Differences in the microbial community functional profiles between plant species were only found for saturated CWs. Biofilm microbial metabolic richness was generally statistically higher than that of interstitial water in both unsaturated (1.4-24 times higher) and saturated (1.2-1.7 times higher) CWs. Carbon source (guild) utilization patterns were generally different between interstitial water and biofilm samples. Functionality of the biofilm microbial community was positively correlated to the removal of all pollutants (TN, NH4+-N, TP, TOC and tebuconazole) for both unsaturated and saturated CWs, suggesting the biofilm plays a more important role in pollutant removal than the interstitial water microbial community. Thus, merely observing the interstitial water microbial communities may underestimate the role of the microbial community in CW performance. Interestingly, the ability for the biofilm microbial community to utilize amino acids and amines/amides was positively correlated with tebuconazole removal in all system types.

Multi-family methodologies for the analysis of veterinary pharmaceutical compounds in sediment and sludge samples: comparison among extraction techniques

Veterinary drugs are still poorly studied in terms of pathways, release rates and effects on the environment. So, it is necessary to determine their levels in sewage sludge and soil/sediments affected by wastewaters. However, published methodologies deal usually with compounds from only a few classes. In addition, there is a lack of comparisons among the different extraction technologies used. A multi-family methodology for the simultaneous determination of minocycline, oxytetracycline, tetracycline (tetracyclines), enrofloxacin (fluoroquinolone) and ceftiofur (cephalosporin) in sludge and sediment was pursued. Three extraction techniques were compared, vortex agitation, ultrasonic extraction (USE) and microwave assisted extraction. Introduction of solid-phase extraction (SPE) for sample clean-up and pre-concentration was also evaluated. The complex matrix of solid samples posed specific problems, implying the need for individualized approaches for sediments and sludge. For sediments, USE sequential extraction (2 cycles) with methanol–acetone was chosen. LODs, when using SPE, ranged from 0.009 to 0.02 μg g−1. For sludge, samples were sequentially extracted three times by USE with methanol–formic acid. The SPE allowed lowering the limits 10 times ranging from 0.08 to 0.3 μg g−1 for LODs. The method yielded good selectivity and acceptable recovery results. The present methodology resulted in suitable multi-family approaches, less common than the majority of similar processes published.