Antioxidant, Antimicrobial, Cytotoxicity, and Larvicidal Activities of Selected Synthetic Bis-Chalcones.

Plants are known to have numerous phytochemicals and other secondary metabolites with numerous pharmacological and biological properties. Among the various compounds, polyphenols, flavonoids, anthocyanins, alkaloids, and terpenoids are the predominant ones that have been explored for their biological potential. Among these, chalcones and bis-chalcones are less explored for their biological potential under in vitro experiments, cell culture models, and animal studies. In the present study, we evaluated six synthetic bis-chalcones that were different in terms of their aromatic cores, functional group substitution, and position of substitutions. The results indicated a strong antioxidant property in terms of DPPH and ABTS radical-scavenging potentials and ferric-reducing properties. In addition, compounds 1, 2, and 4 exhibited strong antibacterial activities against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Salmonella enteritidis. The disc diffusion assay values were indicative of the antibacterial properties of these compounds. Overall, the study indicated the antioxidant and antimicrobial properties of the compounds. Our preliminary studies point to the potential of this class of compounds for further in vivo investigation.

Modulation of Antioxidant Defense in Farmed Rainbow Trout (Oncorhynchus mykiss) Fed with a Diet Supplemented by the Waste Derived from the Supercritical Fluid Extraction of Basil (Ocimum basilicum).

Phytotherapy is based on the use of plants to prevent or treat human and animal diseases. Recently, the use of essential oils and polyphenol-enriched extracts is also rapidly increasing in the aquaculture sector as a means of greater industrial and environmental sustainability. Previous studies assessed the antibacterial and antiparasitic effects of these bioactive compounds on fish. However, studies on the modulation of oxidative stress biomarkers are still scant to date. Thus, in this study, the modulation of antioxidant defense against oxidative stress exerted by fish diets supplemented with a basil supercritical extract (F1-BEO) was assessed in rainbow trout Oncorhynchus mykiss. The F1-BEO extracted with supercritical fluid extraction was added to the commercial feed flour (0.5, 1, 2, 3% w/w) and mixed with fish oil to obtain a suitable compound for pellet preparation. Fish were fed for 30 days. The levels of stress biomarkers such as superoxide dismutase, catalase, glutathione peroxidase, glutathione S-transferase, glutathione reductase, glyoxalase I, glyoxalase II, lactate dehydrogenase, glutathione and malondialdehyde showed a boost in the antioxidant pathway in fish fed with a 0.5% F1-BEO-supplemented diet. Higher F1-BEO supplementation led to a failure of activity of several enzymes and the depletion of glutathione levels. Malondialdehyde concentration suggests a sufficient oxidative stress defense against lipid peroxidation in all experimental groups, except for a 3% F1-BEO-supplemented diet (liver 168.87 ± 38.79 nmol/mg prot; kidney 146.86 ± 23.28 nmol/mg prot), compared to control (liver 127.76 ± 18.15 nmol/mg prot; kidney 98.68 ± 15.65 nmol/mg prot). Our results suggest supplementing F1-BEO in fish diets up to 0.5% to avoid potential oxidative pressure in farmed trout.

Chemical Composition, Insecticidal and Mosquito Larvicidal Activities of Allspice (Pimenta dioica) Essential Oil.

Essential oils are biologically and environmentally safe pesticidal compounds yielded from aromatic plants. Spices are important sources of essential oils, and they are widely used in the medicine, food, and various other industries. Among the different spices, Allspice (Pimenta dioica) is underexplored in terms of its biological efficacy and a limited number of studies are available on the chemical composition of Allspice essential oil (AEO); thus, the present study evaluated the larvicidal property, the repellency, and the fumigant toxicity against common pests of stored products of AEO. AEO was found to inhibit the survival of larvae of such vectors as Aedis, Culex, and Armigeres species. Further, AEO was found to exert repellant effects against the pests of such stored products as Sitophilus, Callosobruchus, and Tribolium. Similarly, the fumigant toxicity was found to be high for AEO against these species. The contact toxicity of AEO was high against Sitophilus and Callosobruchus. Apart from that, the essential oil was found to be safe against a non-target organism (guppy fishes) and was found to be non-genotoxic in an Allium cepa model. Overall, the results of the present study indicate that the essential oil from Allspice could be used as an environmentally safe larvicidal and biopesticidal compound.

Phyco-remediation of swine wastewater as a sustainable model based on circular economy.

Pork production has expanded in the world in recent years. This growth has caused a significant increase in waste from this industry, especially of wastewater. Although there has been an increase in wastewater treatment, there is a lack of useful technologies for the treatment of wastewater from the pork industry. Swine farms generate high amounts of organic pollution, with large amounts of nitrogen and phosphorus with final destination into water bodies. Sadly, little attention has been devoted to animal wastes, which are currently treated in simple systems, such as stabilization ponds or just discharged to the environment without previous treatment. This uncontrolled release of swine wastewater is a major cause of eutrophication processes. Among the possible treatments, phyco-remediation seems to be a sustainable and environmentally friendly option of removing compounds from wastewater such as nitrogen, phosphorus, and some metal ions. Several studies have demonstrated the feasibility of treating swine wastewater using different microalgae species. Nevertheless, the practicability of applying this procedure at pilot-scale has not been explored before as an integrated process. This work presents an overview of the technological applications of microalgae for the treatment of wastewater from swine farms and the by-products (pigments, polysaccharides, lipids, proteins) and services of commercial interest (biodiesel, biohydrogen, bioelectricity, biogas) generated during this process. Furthermore, the environmental benefits while applying microalgae technologies are discussed.

Development and validation of a methodology for quantifying parts-per-billion levels of arsine and phosphine in nitrogen, hydrogen and liquefied petroleum gas using a variable pressure sampler coupled to gas chromatography-mass spectrometry.

The reliable determination of arsine (AsH3) and phosphine (PH3) in hydrogen (H2), nitrogen (N2) and liquefied petroleum gas (LPG) is of great importance because of its drastic effects on the efficiency of catalysts, as well as the strict regulations associated with health, safety and environmental issues. It is challenging for an analyst to determine the parts per billion of AsH3 and PH3 in H2, N2, and LPG at low and high pressures without collection procedures using adsorption, desorption, and dissolution techniques. To overcome this analytical need an analytical methodology was developed, employing a variable pressure sampler (VPS) coupled to a gas chromatograph (GC) with mass spectrometry (MS) for the identification and quantification of traces of AsH3 and PH3. The instrumentation, tubing and accessories of the VPS were made of passivated steel to avoid losses from absorption of AsH3 and PH3 in the steel which would generate significant analytical problems. The VPS had a homogeneous heating block that prevented analyte losses from condensation. With the VPS, 24 AsH3 and PH3 standards were prepared between 0.005 and 0.1 mg kg-1 in balance of H2, N2 and LPG. The separation and quantification of the analytes was achieved with an improved GC with 4 valves and 5 columns in series that guaranteed the elimination of impurities. The proposed method was optimized in VPS and GC-MS and then validated showing highly accaptable linearity (r2 > 0.9999), detection limits (<0.0009 mg kg-1), limits of quantification (<0.003 mg kg-1), intra-day and inter-day precision and accuracy (<1.14% and ≤3.0% respectively), recovery for the standard addition (86-109%), P values> 0.05 for the test Student's t paired who evaluated the effect of the matrix on pressure and concentration. The speed of analysis was high (<5.2 min). The method was applied to real samples, showing values between 0.005 and 0.1 mg kg-1 and an effect on the efficiency of the Ziegler Natta catalyst between 5 and 56%.

Quantification and elimination of substituted synthetic phenols and volatile organic compounds in the wastewater treatment plant during the production of industrial scale polypropylene.

Substituted synthetic phenols and VOC as industrial waste in water and gases from a polypropylene (PP) production plant were the focus of this research. The scope of the study included two levels of the process which were: extrusion and desorber. A total of 264 samples were taken of the liquid and gas affluent and effluent. Waste water and residual gases were collected during the processing of 6 grades of PP with melt flow index of 25, 20, 15, 10, 2 and 1. The monitoring programs were carried out over the course of a year and the samples were taken at different times in order to evaluate the stability and magnitude of a possible environmental impact of the process. Five phenols were identified in the wastewater and a total of 41 VOCs were found in the gas sample. The selection of these phenols was based principally on their high consumption given the need to improve the thermo-oxidative properties of the PP. For the study of the VOC, a new methodology was developed permitting simultaneous analysis by GC-MS/PDHID/FID combining 7 valves, 8 columns and 3 detectors. In the past the wastewaters were treated with solid phase extraction cartridges and the substituted phenols were analyzed by HPLC with DAD. In the VOCs 7 alkanes, 8 alkenes, 2 alkynes, 7 alcohols, 4 ketones, 2 carboxylic acids, 4 permanent gases, 4 sulfides and 3 thiols were detected. The 5 phenols identified were Irganox 1076, DTF, Etanox 330, Irganox 1010 and Cyanox 1790, and the highest concentrations of each one of these were identified in wastewater from the cutting of pellets with values of 380, 366, 396, 331 y 330 ppm respectively. The wastewater from the desorber showed the highest values for Irganox 1076 and DTF with maximum levels of 250 and 213 ppm respectively. These maximum values were obtained after processing the PP with a melt flow index of 25. The grades with fluidity of 1 and 2 generated the least migration of these phenols to the wastewater. The two industrial wastewater samples were transported to the wastewater treatment plant where the Irganox 1076 and the DTF were completely eliminated in the treatment process. The concentrations of Irganox 1010, Cyanox 1790 and Ethanox 330 were reduced over 90%.

An automated on-line turbulent flow liquid-chromatography technology coupled to a high resolution mass spectrometer LTQ-Orbitrap for suspect screening of antibiotic transformation products during microalgae wastewater treatment.

The evaluation of wastewater treatment capabilities in terms of removal of water pollutants is crucial when assessing water mitigation issues. Not only the monitoring of target pollutants becomes a critical point, but also the transformation products (TPs) generated. Since these TPs are very often unknown compounds, their study in both wastewater and natural environment is currently recognized as a tedious task and challenging research field. In this study, a novel automated suspect screening methodology was developed for a comprehensive assessment of the TPs generated from nine antibiotics during microalgae water treatment. Three macrolides (azithromycin, erythromycin, clarithromycin), three fluoroquinolones (ofloxacin, ciprofloxacin, norfloxacin) and three additional antibiotics (trimethoprim, pipemidic acid, sulfapyridine) were selected as target pollutants. The analysis of samples was carried out by direct injection in an on-line turbulent flow liquid chromatography-high resolution mass spectrometry (TFC-LC-LTQ-Orbitrap-MS/MS) system, followed by automatic data processing for compound identification. The screening methodology allowed the identification of 40 tentative TPs from a list of software predicted intermediates created automatically. Once known and unknown TPs were identified, degradation pathways were suggested considering the different mechanisms involved on their formation (biotic and abiotic). Results reveal microalgae ability for macrolide biotransformation, but not for other antibiotics such as for fluoroquinolones. Finally, the intermediates detected were included into an in-house library and applied to the identification of tentative TPs in real toilet wastewater treated in a microalgae based photobioreactor (PBR). The overall approach allowed a comprehensive overview of the performance of microalgae water treatment in a fast and reliable manner: it represents a useful tool for the rapid screening of wide range of compounds, reducing time invested in data analysis and providing reliable structural identification.

Five-year monitoring of 19 illicit and legal substances of abuse at the inlet of a wastewater treatment plant in Barcelona (NE Spain) and estimation of drug consumption patterns and trends.

Illicit and legal drugs of abuse, including alcohol, continue to be in the focus of many governmental national and international studies due to the important consequences of their consumption at both individual and social level. Estimation of drug use at the community level from the concentrations of the drugs themselves or their major metabolites measured in wastewater has become an increasingly accepted and extended tool, complementary to the methods traditionally used for this purpose. The present work describes the application of this approach, generally known as wastewater epidemiology, to investigate the latest drug consumption patterns and trends in the European city of Barcelona. To this end, a total of 19 selected drugs of abuse and metabolites were monitored at the inlet of one of the main wastewater treatment plants of Barcelona every day during one week in March between 2011 and 2015. Analysis of the selected drugs and metabolites in the wastewater samples was performed by means of two methodologies based on liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the concentrations obtained were translated into consumption data. In agreement with official records, alcohol, followed by cannabis, cocaine, amphetamine-like compounds, and methadone were the most consumed drugs. Alcohol, cannabis, and cocaine consumption were on average 18mL(14g)/day/inhabitant (>15), 38g/day/1000 inhabitants aging 15-64, and 2.4g/day/1000 inhabitants aging 15-64, respectively. As for drug use trends, consumption increased over the 5years monitored for all drugs, but for heroin and diazepam. Weekly profiles characterized by higher consumption over the weekend as compared to weekdays were observed only for alcohol, cocaine, and MDMA. Extrapolation of the data obtained for the area under study to the national Spanish territory yields consumption figures of 142t of illicit drugs per year and >2500 million euro turnover per year in the black market.

Chemical and toxicological characterisation of anticancer drugs in hospital and municipal wastewaters from Slovenia and Spain.

Anticancer drugs are continuously released into hospital and urban wastewaters, where they, most commonly, undergo conventional treatment in wastewater treatment plants (WWTPs). Wastewaters contain complex mixtures of substances including parent compounds, their metabolites and transformation products (TPs). In this study, samples of hospital effluents and WWTP influents and effluents from Slovenia and Spain were analyzed for twenty-two selected anticancer drugs, their metabolites and transformation products. Acute and chronic toxicity tests were performed on the crustacean Ceriodaphnia dubia, genotoxicity was determined with Tradescantia and Allium cepa micronucleus (MN) assays and in vitro comet assay in zebrafish (Danio rerio) liver cell line (ZFL cells). Sixty of the two hundred-twenty determinations revealed detectable levels of anticancer drug residues. Among the targeted compounds, platinum based were most frequently detected (90%). Furthermore, erlotinib was detected in 80%, cyclophosphamide and tamoxifen in 70% and methotrexate in 60% of the samples. Seven of ten samples were toxic to C. dubia after acute exposure, whereas after chronic exposure all samples reduced reproduction of C. dubia at high sample dilutions. Allium cepa proved insensitive to the potential genotoxicity of the tested samples, while in Tradescantia increased MN frequencies were induced by a hospital effluent and WWTP influents. In ZFL comet assay all but one sample induced a significant increase of DNA strand breaks. Correlations of chemotherapeutics or their TPs were detected for all bioassays except for Allium cepa genotoxicity test, however for each test the highest correlations were found for different substances indicating differential sensitivities of the test organisms.

Removal of antibiotics in wastewater by enzymatic treatment with fungal laccase - Degradation of compounds does not always eliminate toxicity.

In this study, the performance of immobilised laccase (Trametes versicolor) was investigated in combination with the mediator syringaldehyde (SYR) in removing a mixture of 38 antibiotics in an enzymatic membrane reactor (EMR). Antibiotics were spiked in osmosed water at concentrations of 10µg·L(-1) each. Laccase without mediator did not reduce the load of antibiotics significantly. The addition of SYR enhanced the removal: out of the 38 antibiotics, 32 were degraded by >50% after 24h. In addition to chemical analysis, the samples' toxicity was evaluated in two bioassays (a growth inhibition assay and the Microtox assay). Here, the addition of SYR resulted in a time-dependent increase of toxicity in both bioassays. In cooperation with SYR, laccase effectively removes a broad range of antibiotics. However, this enhanced degradation induces unspecific toxicity. If this issue is resolved, enzymatic treatment may be a valuable addition to existing water treatment technologies.

Identification of markers of cancer in urban sewage through the use of a suspect screening approach.

The administration of anticancer drugs during chemotherapy treatments has increased considerably in recent years, and based on the growing incidence of cancer worldwide there is a foreseen increase in their use over the coming years. Many anticancer drugs are not removed by conventional wastewater treatment plants (WWTPs) and can therefore reach the aquatic environment and potentially threaten aquatic life. The objective of this work was to apply a suspect screening methodology to detect chemotherapy and radiotherapy drugs and their related compounds such metabolites and/or biomarkers in wastewater. The use of logical pre-determined criteria to refine the suspect list down to a relatively small number of relevant compounds greatly improved the efficiency of the analysis. Mass accuracy, isotopic patterns and predicted retention time were used to tentatively identify the suspects. Successful identification of cancer-related suspects included two antineoplastic hormones, two X-ray contrast agents and a pyrrolizidine alkaloid related to an herbal medicine. This is the first time that a suspect screening paradigm has been successfully applied to the identification of pharmaceuticals and biomarkers related to chemotherapy in wastewater.

Ecotoxicity of sediments in rivers: Invertebrate community, toxicity bioassays and the toxic unit approach as complementary assessment tools.

The determination of the real toxicity of sediments in aquatic ecosystems is challenging and necessary for an appropriate risk assessment. Different approaches have been developed and applied over the last several decades. Currently, the joint implementation of chemical, ecological and toxicological tools is recommended for an appropriate and successful toxicity risk assessment. We chose the combination of the toxic unit approach with acute pore water tests (Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna) and whole-sediment exposure tests (V. fischeri, Chironomus riparius), together with invertebrate community composition (multivariate analyses) to detect short and long-term responses of the organisms in four rivers of the Iberian Peninsula. High toxicity was detected in three sites (the downstream sites of the Llobregat and the Júcar, and the most upstream site of the Ebro). We identified organophosphate insecticides and metals as the main variables responsible for this toxicity, particularly in the whole-sediment tests. In particular, chlorpyrifos was mostly responsible for the toxicity (TUs) of D. magna, coinciding with the C. riparius mortality (long-term toxicity) in the mentioned sites, and copper was the main pollutant responsible for the short-term toxicity of P. subcapitata. The combination of the different approaches allowed us to detect ecotoxicological effects in organisms and identify the main contributors to the toxicity in these multi-stressed rivers.

Characterization of ciprofloxacin-resistant isolates from a wastewater treatment plant and its receiving river.

In this study we characterised the ciprofloxacin-resistant strains isolated in biofilm and sediments from a wastewater treatment plant (WWTP) discharge point and its receiving river. We also examined the prevalence of qnrA, qnrB, qnrS and aac(6')-Ib-cr genes in these isolates and determined whether they harbour plasmid-encoded ß-lactamases such as TEM, SHV and CTX-M. Moreover, antibiotic concentrations were also measured to evaluate the level of contamination of these pharmaceuticals in the sampling area. Antibiotics were found in the range of ng L(-1) in WWTP effluents, but most of them were no longer found in downstream river. However, some fluoroquinolones were detected in sediment downstream demonstrating their high persistence and their capacity to be retained in the river sediments. Most of the ciprofloxacin-resistant isolates belonged to the Gammaproteobacteria class and 17 of them, 8 (7.6%) from the first sampling and 9 (6.1%) from the second sampling, carried a qnr gene. In particular, 15 isolates carried the qnrS gene and 2 carried the qnrB gene. Among the qnr-positive isolates, 12 harboured the aac(6')-lb-cr gene and 2 of them also carried a ß-lactamase on the same plasmid, indicating that they may be transferred simultaneously. It is also noteworthy that all qnr-positive isolates identified as Aeromonas species harboured the same qnrS allele, namely the qnrS2. This study reinforces the importance of environmental bacteria as vehicles for dissemination of antibiotic resistance genes.

Solid-phase treatment with the fungus Trametes versicolor substantially reduces pharmaceutical concentrations and toxicity from sewage sludge.

For safe biosolid-land-applying, sludge should be contaminant-free. However, it may contain important amounts of micropollutants, not removed in the wastewater-treatment-processes. An alternative treatment with the fungus Trametes versicolor was applied in sterile solid-phase systems consisting of sludge and a lignocellulosic substrate. Fungal colonization and activity were demonstrated during the process, according to monitoring of ergosterol, laccase activity and the naproxen-degradation test (ND24). Fourteen out of 43 analyzed pharmaceuticals were found in the raw sludge. After treatment, phenazone, bezafibrate, fenofibrate, cimetidine, clarithromycin, sulfamethazine and atenolol were completely removed, while removals between 42% and 80% were obtained for the remaining pharmaceuticals. Toxicological analyses (Daphnia magna, Vibrio fischeri and seed germination) showed an important reduction in sludge toxicity after treatment. Results suggest that a solid-phase treatment with T. versicolor may reduce the ecotoxicological impact of micropollutants present in sewage sludge. This is the first report of a fungal-approach for elimination of emerging pollutants from biosolids.

Diastereoisomer- and enantiomer-specific determination of hexabromocyclododecane in fish oil for food and feed.

Fish oils are one of the main sources of ω-3 fatty acids. However, they can present elevated levels of some lipophilic pollutants, such as hexabromocyclododecanes (HBCDs). Since data about HBCDs in fish oil samples are very limited, in this study, 25 samples of fish oil for feed and food have been analyzed. Total HBCDs, as well as, α-, ß- and γ-diastereoisomers have been determined. Total HBCDs ranged from 0.09 to 26.8ngg(-1), with higher concentrations in fish oil for feed (average value of 9.69ngg(-1)) than those for food (1.14ngg(-1)). Concentrations of α-HBCD (average value of 4.12ngg(-1) in feed samples and 0.48ngg(-1) in food samples) and γ-HBCD (5.05 and 0.43ngg(-1) respectively) were higher than that of ß-HBCD (0.52 and 0.19ngg(-1) respectively) in most of the samples. However, none of them was predominant in the samples. Concentrations of HBCDs were compared to concentrations of other pollutants and correlation between dioxin and dioxin-like PCBs levels and HBCDs levels were observed. Intake of HBCDs was calculated for fish oil with human consumption purposes and it ranged from 0.08 to 5.38ng HBCDsd(-1), which could contribute significantly to HBCDs total intake. Enantiomeric fractions were also determined. No clear enrichment was observed for γ-HBCD, while (-)-α-HBCD enrichment was detected in some samples.

Drugs of abuse and their metabolites in the Ebro River basin: occurrence in sewage and surface water, sewage treatment plants removal efficiency, and collective drug usage estimation.

Drugs of abuse and their metabolites have been recently recognized as environmental emerging organic contaminants. Assessment of their concentration in different environmental compartments is essential to evaluate their potential ecotoxicological effects. It also constitutes an indirect tool to estimate drug abuse by the population at the community level. The present work reports for the first time the occurrence of drugs of abuse and metabolites residues along the Ebro River basin (NE Spain) and also evaluates the contribution of sewage treatment plants (STPs) effluents to the presence of these chemicals in natural surface waters. Concentrations measured in influent sewage waters were used to back calculate drug usage at the community level in the main urban areas of the investigated river basin. The most ubiquitous and abundant compounds in the studied aqueous matrices were cocaine, benzoylecgonine, ephedrine and ecstasy. Lysergic compounds, heroin, its metabolite 6-monoacetyl morphine, and Delta(9)-tetradhydrocannabinol were the substances less frequently detected. Overall, total levels of the studied illicit drugs and metabolites observed in surface water (in the low ng/L range) were one and two orders of magnitude lower than those determined in effluent (in the ng/L range) and influent sewage water (microg/L range), respectively. The investigated STPs showed overall removal efficiencies between 45 and 95%. Some compounds, such as cocaine and amphetamine, were very efficiently eliminated (>90%) whereas others, such as ecstasy, methamphetamine, nor-LSD, and THC-COOH where occasionally not eliminated at all. Drug consumption estimates pointed out cocaine as the most abused drug, followed by cannabis, amphetamine, heroin, ecstasy and methamphetamine, which slightly differs from national official estimates (cannabis, followed by cocaine, ecstasy, amphetamine and heroin). Extrapolation of the consumption data obtained for the studied area to Spain points out a total annual consumption of drugs of abuse of the order of 36 tonnes, which would translate into 1100million Euros in the black market.

Microwave-assisted extraction and ultrasonic extraction to determine polycyclic aromatic hydrocarbons in needles and bark of Pinus pinaster Ait. and Pinus pinea L. by GC-MS.

Two different extraction strategies (microwave-assisted extraction (MAE) and ultrasonic extraction (USE)) were tested in the extraction of the 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from pine trees. Extraction of needles and bark from two pine species common in the Iberian Peninsula (Pinus pinaster Ait. and Pinus pinea L.) was optimized using two amounts of sample (1g and 5 g) and two PAHs spiking levels (20 ng/g and 100 ng/g). In all cases, the clean-up procedure following extraction consisted in solid-phase extraction (SPE) with alumina cartridges. Quantification was done by gas chromatography (GC) with mass spectrometry (MS), using five deuterated PAH surrogate standards as internal standards. Limits of detection were globally below 0.2 ng/g. The method was robust for the matrices studied regardless of the extraction procedures. Recovery values between 70 and 130% were reached in most cases, except for high molecular weight PAHs (indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[ghi]perylene). A field study with naturally contaminated samples from eight sites (four in Portugal and four in Catalonia, Spain) showed that needles are more suitable biomonitors for PAHs, yielding concentrations from 2 to 17 times higher than those found in bark. The levels varied according to the sampling site, with the sum of the individual PAH concentrations between 213 and 1773 ng/g (dry weight). Phenanthrene was the most abundant PAH, followed by fluoranthene, naphthalene and pyrene.

Analysis of biologically active compounds in water by ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry.

A new method based on ultra-performance liquid chromatography (UPLC) quadrupole time-of-flight mass spectrometry ((Q-ToF)-MS) was developed for the analysis of 32 biologically active compounds including anti-inflammatories, analgesics, lipid regulators, psychiatric drugs, anti-ulcer agents, antibiotics, beta-blockers and phytoestrogens. This new method allows chromatographic analysis in 14 min, with instrumental detection limits from 2 to 84 pg, and limits of quantification ranging from 0.1 to 15 ng/L in tap water, and from 2 to 300 ng/L in wastewater. The potential of liquid chromatography with triple quadrupole mass spectrometry (LC/QqQ-MS) was compared with that of UPLC/(Q-ToF)-MS for the analysis of biologically active compounds in water samples. LC/Q-ToF provides accurate mass information and a significantly higher mass resolution than quadrupole analyzers. The available mass resolution of ToF instruments diminishes the problem of isobaric interferences and helps the analysis of trace compounds in complex samples. In this work UPLC/Q-ToF chromatograms were recorded containing full scan spectral data. The m/z values of analytes were extracted from the total ion chromatogram (TIC) and the accurate masses of the compounds were obtained. In addition, to increase the selectivity of ToF measurements a narrow accurate mass interval (20 m m/z units mass window) was used to reconstruct the chromatographic traces. However, regarding quantitative performance in terms of dynamic range and limits of detection (LODs), typical LODs achieved by QqQ instruments operating in multiple-reaction monitoring (MRM) mode ranged from 1 to 50 ng/L in wastewater, and the linear response for QqQ instruments generally covers three orders of magnitude. This is an important advantage over ToF instruments and one of the reasons why QqQ instruments are widely used in quantitative environmental analysis.

Comparison of sulfonated and other micropollutants removal in membrane bioreactor and conventional wastewater treatment.

Membrane bioreactors (MBRs) were compared with conventional activated sludge systems (CAS) for micropollutant degradation, in laboratory-scale spiking experiments with synthetic and real domestic wastewater. The target micropollutants were polar in nature and represented a broad range in biodegradability. The experimental data indicated that MBR treatment could significantly enhance removal of the micropollutants 1,6- and 2,7-naphthalene disulfonate (NDSA) and benzothiazole-2-sulfonate. 1,5-NDSA, EDTA and diclofenac were not removed in either the MBR or the CAS. The other compounds were equally well degraded in both systems. For 1,3-naphthalene disulfonate, the existence of a minimum threshold level for degradation could be demonstrated. Although MBRs could not always make a difference in the overall removal efficiencies achieved, they showed reduced lag phases for degradation and a stronger memory effect, which implies that they may respond quicker to variable influent concentrations. Finally, micropollutant removal also turned out to be less sensitive to system operational variables.