ABSTRACT
This study aimed on the development of a SPE-UHPLC-MS/MS method for the simultaneous determination of pesticide residues in drinking water samples. A chemometric approach was applied to optimize the efficiency of the SPE pretreatment procedure. This study involved (i) the application of a Full Factorial Design for the screening of the significant factors, (ii) the application of a Central Composite Design for the determination of the optimal conditions and (iii) the evaluation and validation of the significance of the statistically proposed models. Oasis HLB cartridges were used for the extraction. The optimum sample volume was 300 mL and the elution solvent 3 mL of the mixture of methanol:ethylacetate 70:30 v/v. The method was validated according to the international guidelines. Recoveries were ranged from 63 to 116% and the detection limits were between 0.1 and 1.5 pg mL- 1. The validated method could be used in routine analysis for pesticides screening.
Subject(s)
Pesticides , Pesticides/analysis , Tandem Mass Spectrometry/methods , Chromatography, High Pressure Liquid/methods , Chemometrics , Solid Phase Extraction/methods , WaterABSTRACT
In the present study, the application and evaluation of Girard's Reagent T (GRT) derivatization for the simultaneous detection and significantly important identification of different phase II methenolone and mesterolone metabolites by LC-MS/(MS) are presented. For the LC-MS analysis of target analytes two complementary isolation methods were developed; a derivatization and shoot method in which native urine is diluted with derivatization reagent and is injected directly to LC-MS and a liquid-liquid extraction method, using ethyl acetate at pH 4.5, for the effective isolation of both sulfate and glucuronide metabolites of the named steroids as well as of their free counterparts. For the evaluation of the proposed protocols, urine samples from methenolone and mesterolone excretion studies were analyzed against at least one sample from a different excretion study. Retention times, along with product ion ratios, were evaluated according to the WADA TD2021IDCR requirements, in order to determine maximum detection and identification time windows for each metabolite. Established identification windows obtained after LC-MS/(MS) analysis were further compared with those obtained after GC-MS/(MS) analysis of the same samples from the same excretion studies, for the most common analytes monitored by GC-MS/(MS). Full validation was performed for the developed derivatization and shoot method for the identification of methenolone metabolite, 3α-hydroxy-1-methylen-5α-androstan-17-one-3-glucuronide (mth3). Overall, the GRT derivatization presented herein offers a tool for the simultaneous sensitive detection of free, intact glucuronide and sulfate metabolites by LC-MS/(MS) that enhance significantly the detection and identification time windows of specific methenolone and mesterolone metabolites for doping control analysis.
Subject(s)
Mesterolone , Methenolone , Mesterolone/metabolism , Methenolone/metabolism , Chromatography, Liquid/methods , Glucuronides/urine , Tandem Mass Spectrometry/methods , Sulfates/urineABSTRACT
Contemporary wastewater reclamation units entail several diverse treatment and extraction processes, with a multitude of monitored quality characteristics, controlled by a variety of key operational parameters directly affecting the efficiency of treatment. The conventional optimization of this highly complex system is time- and energy- consuming, frequently relying on intuitive decision making by operators, and does not predict or forecast efficiency changes and system maintenance. In this paper, we introduce intelligent solutions to enhance the operational control of the unit with minimal human intervention and to develop an AI-powered DSS that is installed atop the sensors of a water treatment module. The DSS uses an expert model, both to assess the quality of water and to offer suggestions based on current values and future trends. More specifically, the quality of the produced water was successfully visualized, assessed and rated, based on a set of input operational variables (pH, TOC for this case), while future values of monitored sensors were forecasted. Additionally, monitoring services of the DSS were able to identify unexpected events and to generate alerts in the case of observed violation of operational limits, as well as to implement changes (automatic responses) to operational parameters so as to reestablish normal operating conditions and to avoid such events in the future. Up to now, the DSS suggestion and forecasting services have proven to be adequately accurate. Though data are still being collected from early adopters, the solution is expected to provide a complete water treatment solution that can be adopted by a vast range of parties.
Subject(s)
Wastewater , Water Purification , Humans , Waste Disposal, FluidABSTRACT
Low back pain is a major chronic musculoskeletal disorder, caused mainly due the degeneration of the intervertebral discs (IVDs). Bisphosphonates (BPs), like zoledronic acid (ZOL), are used in osteoporosis management; however, their accumulation in the IVDs and their physiological role has not been addressed so far. To this end, an SPE-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) analytical method, using on-cartridge derivatization, has been developed and validated. The analytical method presented excellent linearity (R2 > 0.992), high recoveries (67.8-82.6%), increased repeatability (0.5-9.9%) and low LOD values (21 ng g-1 in the case of IVDs) in all matrices studied. The injection of ZOL in a rabbit animal model resulted in rapid accumulation in blood plasma and the skin, followed by quick clearance. On the other hand, no ZOL was detected in nucleus pulposus, the core of the IVD, while in the peripheral annulus fibrosus a lower and delayed accumulation, as well as dispersal was found. These variations are most probably due to the avascular nature of IVD, allowing only the diffusion of small molecules in and out of the tissue, and/or to the unique physicochemical environment of IVDs. Finally, ZOL, at the concentrations found, did not affect cells' viability or the increase of reactive oxygen species (ROS).
Subject(s)
Intervertebral Disc , Nucleus Pulposus , Animals , Chromatography, Liquid , Rabbits , Tandem Mass Spectrometry , Zoledronic AcidABSTRACT
Lake Karaoun is the largest artificial lake in Lebanon and serves multiple purposes. Recently, intensive cyanobacterial blooms have been reported in the lake, raising safety and aesthetic concerns related to the presence of cyanotoxins and cyanobacterial taste and odor (T&O) compounds, respectively. Here, we communicate for the first time results from a recent investigation by LC-MS/MS covering multiple cyanotoxins (microcystins (MCs), anatoxin-a, cylindrospermopsin, nodularin) in water and fish collected between 2019 and 2020. Eleven MCs were identified reaching concentrations of 211 and 199 µg/L for MC-LR and MC-YR, respectively. Cylindrospermopsin, anatoxin-a and nodularin were not detected. The determination of the total MCs was also carried out by ELISA and Protein Phosphatase Inhibition Assay yielding comparable results. Molecular detection of cyanobacteria (16S rRNA) and biosynthetic genes of toxins were carried out by qPCR. Untargeted screening analysis by GC-MS showed the presence of T&O compounds, such as ß-cyclocitral, ß-ionone, nonanal and dimethylsulfides that contribute to unpleasant odors in water. The determination of volatile organic compounds (VOCs) showed the presence of anthropogenic pollutants, mostly dichloromethane and toluene. The findings are important to develop future monitoring schemes in order to assess the risks from cyanobacterial blooms with regard to the lake's ecosystem and its uses.
Subject(s)
Cyanobacteria Toxins/analysis , Lakes/chemistry , Water Pollutants, Chemical/analysis , Animals , Carps , Cyanobacteria/chemistry , Cyanobacteria/genetics , Cyanobacteria Toxins/genetics , Environmental Monitoring/methods , Eutrophication , Fresh Water/chemistry , Lakes/microbiology , Lebanon , Odorants , RNA, Ribosomal, 16S , Taste , Volatile Organic Compounds/analysisABSTRACT
Cyanotoxins (CTs) produced by cyanobacteria in surface freshwater are a major threat for public health and aquatic ecosystems. Cyanobacteria can also produce a wide variety of other understudied bioactive metabolites such as oligopeptides microginins (MGs), aeruginosins (AERs), aeruginosamides (AEGs) and anabaenopeptins (APs). This study reports on the co-occurrence of CTs and cyanopeptides (CPs) in Lake Vegoritis, Greece and presents their variant-specific profiles obtained during 3-years of monitoring (2018-2020). Fifteen CTs (cylindrospermopsin (CYN), anatoxin (ATX), nodularin (NOD), and 12 microcystins (MCs)) and ten CPs (3 APs, 4 MGs, 2 AERs and aeruginosamide (AEG A)) were targeted using an extended and validated LC-MS/MS protocol for the simultaneous determination of multi-class CTs and CPs. Results showed the presence of MCs (MC-LR, MC-RR, MC-YR, dmMC-LR, dmMC-RR, MC-HtyR, and MC-HilR) and CYN at concentrations of <1 µg/L, with MC-LR (79%) and CYN (71%) being the most frequently occurring. Anabaenopeptins B (AP B) and F (AP F) were detected in almost all samples and microginin T1 (MG T1) was the most abundant CP, reaching 47.0 µg/L. This is the first report of the co-occurrence of CTs and CPs in Lake Vegoritis, which is used for irrigation, fishing and recreational activities. The findings support the need for further investigations of the occurrence of CTs and the less studied cyanobacterial metabolites in lakes, to promote risk assessment with relevance to human exposure.
Subject(s)
Bacterial Toxins/analysis , Cyanobacteria , Peptides/analysis , Water Pollutants/analysis , Chlorophyll A/analysis , Environmental Monitoring , Greece , Lakes/analysis , Lakes/microbiologyABSTRACT
This study presents the development of an analytical method for the simultaneous determination of multiclass illicit drugs (cocainoids, opiates, amphetamines, and cannabinoids) and psychoactive pharmaceuticals (anxiolytics, hypnotics, antipsychotics, antidepressants, and antiparkinsonian), in municipal wastewater. The analytical method was validated in terms of specificity, linearity, precision, and accuracy. The recoveries (%) for the majority of the analytes ranged between 70 and 120%, while the method showed good repeatability (2.4-29.2%). The limits of detection (LOD) of the method ranged between 0.8 and 9.4 ng L-1. The method was implemented on influent and effluent samples from Thessaloniki (N. Greece) wastewater treatment plant (WWTP), and it revealed the daily presence of benzoylecgonine (BEG) (84.0-202.2 ng L-1), methadone (12.3-17.5 ng L-1), 11-Nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) (80.3-171.9 ng L-1), morphine (144.2-264.3 ng L-1), and 6-monoacetylmorphine (6-MAM) (5.8-12.0 ng L-1) in the influent samples of WWTP. Clozapine (101.6-315.5 ng L-1), quetiapine (33.5-109.7 ng L-1), and fluoxetine (20.9-124.4 ng L-1) were pharmaceutical psychotics with the highest concentration in the influents. Back calculation estimated that the daily consumption of cocaine, heroin, cannabis, and methadone was 36-95, 86-164, 2300-5400, and 8-12 mg day-1 per 1000 inhabitants, respectively. The consumption was estimated between 7-16 and 15 mg day-1 per 1000 inhabitants for methyl diethanolamine (MDEA) and 3,4-methylenedioxymethamphetamine (MDMA), respectively.
Subject(s)
Illicit Drugs , Water Pollutants, Chemical , Chromatography, Liquid , Environmental Monitoring , Greece , Solid Phase Extraction , Tandem Mass Spectrometry , Wastewater/analysis , Water Pollutants, Chemical/analysisABSTRACT
The objectives of the present study were: a) to evaluate the photocatalytic degradation of two benzodiazepine pharmaceuticals, alprazolam and diazepam, using Photo-Fenton, b) to optimize the experimental parameters through a central composite experimental design, c) to assess their mineralization and toxicity variations and d) to identify the transformation products during the process and to propose transformation pathways. Response Surface Methodology proved to be a useful tool for the optimization of the degradation process as the statistical coefficients (R2 = 0.967 for alprazolam and R2 = 0.929 for diazepam) showed satisfactory values confirming the adequate correlation between the predicted models and experimental values. Two sets of experimental conditions were proposed taking into consideration criteria related to the reaction rate and the minimum use of iron. Toxicity of the system varied with time after the treatment, indicating the gradual production of transformation products which differ in their toxic potential. Fifteen and twenty-three photocatalytic degradation products were identified for ALP and DZP respectively using LC-(ESI)MS/MS. In the case of ALP, the main degradation reactions included, phenyl-group removal and the opening of the 7-membered ring, while for DZP, degradation occurred through hydroxylation, formation of benzophenone and the opening of the 7-membered cyclic group.
Subject(s)
Pharmaceutical Preparations , Water Pollutants, Chemical , Alprazolam/toxicity , Diazepam/toxicity , Hydrogen Peroxide , Oxidation-Reduction , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysisABSTRACT
The presence of phosphorus (P) and heavy metals (HMs) in surface sediments originating from lakes Volvi, Kerkini, and Doirani (N. Greece), as well as their fractionation patterns, were investigated. No statistically significant differences in total P content were observed among the studied lakes, but notable differences were observed among sampling periods. HM contents in all lakes presented a consistent trend, i.e., Mn > Cr > Zn > Pb > Ni > Cu > Cd, while the highest concentrations were recorded in Lake Kerkini. Most of the HMs exceeded probable effect level value indicating a probable biological effect, while Ni in many cases even exceeded threshold effects level, suggesting severe toxic effects. P was dominantly bound to metal oxides, while a significant shift toward the labile fractions was observed during the spring period. The sum of potentially bioavailable HM fractions followed a downward trend of Mn > Cr > Pb > Zn > Cu > Ni > Cd for most lakes. The geoaccumulation index Igeo values of Cr, Cu, Mn, Ni, and Zn in all lakes characterized the sediments as "unpolluted," while many sediments in lakes Volvi and Kerkini were characterized as "moderately to heavily polluted" with regard to Cd. The descending order of potential ecological risk [Formula: see text] was Cd > Pb > Cu > Ni > Cr > Zn > Mn for all the studied lakes. Ni and Cr presented the highest toxic risk index values in all lake sediments. Finally, the role of mineralogical divergences among lake sediments on the contamination degree was signified.
Subject(s)
Geologic Sediments/analysis , Lakes/analysis , Metals, Heavy/analysis , Phosphorus/analysis , Water Pollutants, Chemical/analysis , Chemical Fractionation , Environmental Monitoring , Geologic Sediments/chemistry , Greece , Lakes/chemistry , Metals, Heavy/chemistry , Metals, Heavy/toxicity , Phosphorus/chemistry , Risk Assessment , Seasons , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/toxicityABSTRACT
BACKGROUND AND AIMS: Wastewater-based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population-normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011-17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data. DESIGN: Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017. SETTING AND PARTICIPANTS: Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries. MEASUREMENTS: Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of Δ9 -tetrahydrocannabinol (11-nor-9-carboxy-Δ9 -tetrahydrocannabinol) were measured in wastewater using liquid chromatography-tandem mass spectrometry. Daily mass loads (mg/day) were normalized to catchment population (mg/1000 people/day) and converted to the number of combined doses consumed per day. Spatial differences were assessed world-wide, and temporal trends were discerned at European level by comparing 2011-13 drug loads versus 2014-17 loads. FINDINGS: Benzoylecgonine was the stimulant metabolite detected at higher loads in southern and western Europe, and amphetamine, MDMA and methamphetamine in East and North-Central Europe. In other continents, methamphetamine showed the highest levels in the United States and Australia and benzoylecgonine in South America. During the reporting period, benzoylecgonine loads increased in general across Europe, amphetamine and methamphetamine levels fluctuated and MDMA underwent an intermittent upsurge. CONCLUSIONS: The analysis of wastewater to quantify drug loads provides near real-time drug use estimates that globally correspond to prevalence and seizure data.
Subject(s)
Environmental Monitoring/methods , Illicit Drugs , Spatio-Temporal Analysis , Substance Abuse Detection/methods , Wastewater/chemistry , Amphetamine/analysis , Chromatography, Liquid , Cocaine/analogs & derivatives , Cocaine/analysis , Humans , Internationality , Methamphetamine/analysis , N-Methyl-3,4-methylenedioxyamphetamine/analysis , Tandem Mass SpectrometryABSTRACT
Cyanobacteria are a diverse group of photosynthetic Gram-negative bacteria that produce an array of secondary compounds with selective bioactivity against a broad spectrum of organisms and cell lines. In this study, 29 strains isolated from freshwaters in Greece were classified using a polyphasic approach and assigned to Chroococcales, Synechococcales, and Nostocales, representing 11 genera and 17 taxa. There were good agreements between 16S ribosomal RNA (rRNA)-cpcBA-internal genetic spacer (IGS) characterization and morphological features, except for the Jaaginema-Limnothrix group which appears intermixed and needs further elucidation. Methanol extracts of the strains were analyzed for cyanotoxin production and tested against pathogenic bacteria species and several cancer cell lines. We report for the first time a Nostoc oryzae strain isolated from rice fields capable of producing microcystins (MCs) and a Chlorogloeopsis fritschii strain isolated from the plankton of a lake, suggesting that this species may also occur in freshwater temperate habitats. Strains with very high or identical 16S rRNA gene sequences displayed different antibacterial and cytotoxic activities. Extracts from Synechococcus cf. nidulans showed the most potent antibacterial activity against Staphylococcus aureus, whereas Jaaginema sp. strains exhibited potent cytotoxic activities against human colorectal adenocarcinoma and hepatocellular carcinoma cells. Jaaginema Thessaloniki Aristotle University Microalgae and Cyanobacteria (TAU-MAC) 0110 and 0210 strains caused pronounced changes in the actin network and triggered the formation of numerous lipid droplets in hepatocellular carcinoma and green monkey kidney cells, suggesting oxidative stress and/or mitochondrial damage leading to apoptosis.
Subject(s)
Bacterial Toxins/analysis , Cyanobacteria/isolation & purification , Animals , Anti-Bacterial Agents/isolation & purification , Anti-Bacterial Agents/pharmacology , Biodiversity , Cell Line , Cell Survival/drug effects , Chlorocebus aethiops , Complex Mixtures/pharmacology , Cyanobacteria/classification , Cyanobacteria/genetics , Fresh Water/microbiology , Greece , Humans , Microalgae/classification , Microalgae/genetics , Microalgae/isolation & purification , Phylogeny , RNA, Ribosomal, 16SABSTRACT
An automated flow method for the determination of hydrazine based on the concept of zone-fluidics has been developed. The analyte reacts under flow conditions with p-dimethylamino benzaldehyde (25 mmol L-1) in micellar medium (100 mmol L-1 SDS) to form a stable derivative (460 nm). Micelles mediated catalysis excludes the use of highly acidic environment typical for this kind of reaction. Following careful examination of chemical and instrumental variables, the method allows the determination of hydrazine at the low micromolar level (0.3-10 µmol L-1) in water samples. Real sample analyses (drinking and boiler feed water) resulted in satisfactory results in terms of accuracy with the percent recoveries being in the range of 82-114%.
Subject(s)
Hydrazines/analysis , Water Pollutants, Chemical/analysis , Benzaldehydes/chemistry , Catalysis , Data Accuracy , Limit of Detection , Micelles , Sodium Dodecyl Sulfate/chemistry , Temperature , Time Factors , Water/chemistryABSTRACT
Toxic cyanobacteria occur in Greek surface water bodies. However, studies on the occurrence of cyanotoxins (CTs) are often limited to mainly microcystins (MCs), with use of screening methods, such as ELISA, that are not conclusive of the chemical structure of the CT variants and can be subject to false positive results. A multi-lake survey in Greece (14 lakes) was conducted in water and biomass, targeted to a wide range of multi-class CTs including MCs, nodularin-R (NOD), cylindrospermopsin (CYN), anatoxin-a (ANA-a) and saxitoxins (STXs), using multi-class/variant LC-MS/MS analytical workflows, achieving sensitive detection, definitive identification and accurate quantitation. A wide variety of CTs (CYN, ANA-a, STX, neoSTX, dmMC-RR, MC-RR, MC-YR, MC-HtyR, dm3MC-LR, MC-LR, MC-HilR, MC-WR, MC-LA, MC-LY, MC-LW and MC-LF), were detected, with MCs being the most commonly occurring. In biomass, MC-RR was the most abundant toxin, reaching 754 ng mg-1 dw, followed by MC-LR (458 ng mg-1 dw). CYN and ANA-a were detected for the first time in the biomass of Greek lakes at low concentrations and STXs in lakes Trichonis, Vistonis and Petron. The abundance and diversity of CTs were also evaluated in relation to recreational health risks, in a case study with a proven history of MCs (Lake Kastoria).
Subject(s)
Bacterial Toxins/analysis , Bacterial Toxins/classification , Cyanobacteria/metabolism , Lakes/chemistry , Lakes/microbiology , Chromatography, Liquid , Cyanobacteria/growth & development , Greece , Tandem Mass SpectrometryABSTRACT
This paper presents the first report of cyanobacteria and cyanotoxins from the South Caucasus region, in particular from Lake Yerevan (Armenia). Microcystis, Dolichospermum and Planktothrix were the key genera identified during the growing season. A trend of a remarkable increase in cyanobacterial densities was observed from 2012 to 2013 exhibiting bloom formation in June (by Nostoc linckia) with the highest values in June and August 2013, reaching up to 695.9*103â¯cells mL-1. Seasonal dependence of cyanobacterial density on temperature, and temperature as a driver for cyanobacterial cells growth and development were suggested. Biogenic nutrients were identified as co-drivers determining species richness and dominance, as well as the distribution of phytoplankton in different parts of the reservoir. Cyanotoxin concentrations in the filtered biomass were reported during July 2012 for both stations of the reservoir (left and right bank). Microcystin-RR (MC-RR) was the most abundant and the most frequently observed cyanotoxin. Lower MC-LR concentrations were identified in all samples from both stations, with the highest values observed at the right bank in July 2012. [D-Asp3]MC-RR, MC-YR, MC-HtyR, [D-Asp3]MC-LR, MC-HilR, MC-WR, MC-LY and MC-LW were also identified in trace levels. Anatoxin-a (ANA) was reported in the samples from both stations during August 2012. Cylindrospermopsin (CYN) was present in trace concentrations in samples from both stations during July and in the sample from the left bank during September.
Subject(s)
Bacterial Toxins/chemistry , Biodiversity , Cyanobacteria/classification , Lakes/chemistry , Lakes/microbiology , Armenia , Bacterial Toxins/metabolism , Cyanobacteria/metabolism , Seasons , TemperatureABSTRACT
The scope of this study was the development, optimization and validation of an analytical method for the determination of selected heavy metals and trace elements (As, Hg, Se, Cd, Cu, Pb, Mn, Fe, Ni, Zn, Cr) in milk powder, using microwave-assisted digestion. A statistical experimental design approach using central composite design (CCD) was carried out, to investigate the effects of three independent pretreatment variables (final digestion temperature (°C), HNO3 concentration (in % w/v), microwave hold time) on the heavy metal recovery of spiked undigested milk powder sample and to calculate the variable factor values which produce the optimum recovery. CCD results revealed that the optimum digestion conditions, with respect to maximum recovery were as follows: temperature 190 °C, HNO3 56.8% w/v, and digestion time of 8.47 min. The method was fully validated. Recoveries for all metals ranged between 92 and 108% while intra-day repeatability was below 6.59% (rsd). A certified reference material (ERM BD 150) that included 8 out of the total 11 heavy metals of the present study (Hg, Se, Cd, Cu, Pb, Mn, Ni, and Zn) was used to test the accuracy of the method where acceptable recovery values ranging between 96 and 107% were obtained. High heavy metal recoveries, short digestion time, and low acid consumption were the advantages of the pretreatment method. The analytical process was successfully applied for the determination of heavy metals in different milk samples from the Greek market. Heavy metal concentrations for Ni, Cr, Pb, Cd, Se, Mn, and Cu measured in this study reached 307, 102, 8.01, 5.96, 60.2, 519, and 438 µg/kg wet weight (ww), respectively. Zn and Fe were found at concentrations ranging 3.21-8.39 and 0.170-10.1 mg/kg ww, respectively. Risk assessment based on the WHO tolerable daily intake levels and the calculated target hazard quotients revealed that the consumption of the selected milk samples is considered safe.
Subject(s)
Environmental Pollutants/analysis , Food Contamination/analysis , Metals, Heavy/analysis , Milk/chemistry , Adult , Animals , Environmental Monitoring , Greece , Humans , Microwaves , Risk AssessmentABSTRACT
Cyanobacterial and algal toxins comprise a large group of harmful metabolites, belonging to different chemical classes, with a variety of chemical structures, physicochemical properties and toxic activities. In this study, a fast, simple and sensitive analytical method was developed for the simultaneous determination of multi-class cyanobacterial and algal toxins in water. The target compounds were: Cylindrospermopsin, Anatoxin-a, Nodularin, 12 Microcystins ([D-Asp3]MC-RR, MC-RR, MC-YR, MC-HtyR, [D-Asp3]MC-LR, MC-LR, MC-HilR, MC-WR, MC-LA, MC-LY, MC-LW and MC-LF), Okadaic acid and Domoic acid. Analytes were determined using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A dual Solid Phase Extraction (SPE) cartridge assembly was applied for the extraction of target compounds from water. Optimized SPE parameters included cartridge material, initial sample pH, sequence of the cartridges in the SPE assembly as well as composition and volume of the elution solvent. The method was validated, providing acceptable mean recoveries and reproducibility for most analytes. Limits of detection were at the ngL-1 level. The method was successfully applied in real lake water samples from Greece, where a wide range of Microcystins were detected for the first time, at concentrations ranging from 0.034 to 63µgL-1.
Subject(s)
Bacterial Toxins/analysis , Chromatography, Liquid/methods , Marine Toxins/analysis , Microcystins/analysis , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Water Pollutants, Chemical/analysis , Bacterial Toxins/chemistry , Bacterial Toxins/classification , Cyanobacteria Toxins , Greece , Lakes/chemistry , Limit of Detection , Marine Toxins/chemistry , Marine Toxins/classification , Microcystins/chemistry , Microcystins/classification , Molecular Structure , Reproducibility of Results , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/classificationABSTRACT
In the present study, an investigation of the mineralogy and morphology, the heavy metal content and the health risk of urban road dusts from the second largest city of Greece was conducted. For this reason road dust samples from selected sites within the city core area were collected. No differences were observed in the mineralogy of road dusts coming from different sampling sites, and they were mainly consisted of quartz and calcite, while an elevated amorphous content was detected. Morphologically road dusts presented Ca-rich, Fe-rich and silicates particles with various shapes and sizes. The mean concentrations of Cd, Cr, Cu, Mn, Ni, Pb and Zn in road dust were 1.76, 104.9, 662.3, 336.4, 89.43, 209 and 452.8 µg g-1, respectively. A series of spatial distribution patterns revealed that the hotspot areas were tended to associate with major road junctions and regions with high traffic. Combination of pollution indexes and statistical analyses (correlation analysis, cluster analysis and principal component analysis) revealed that road dusts have a severe influence by anthropogenic activities. In attempt to identify the source of metals through geostatistical and multivariate statistical analyses, it was concluded as follows: Cr, Cu, Fe and Zn mainly originated from tire/break wear and vehicle abrasions, while Cd, Mn and Pb were mainly related to fuel/oil leakage from automobiles along with oil lubricants and vehicle abrasion. Hazard quotient values for children based on total metal concentrations for the road dust ingestion route were lower than safe level (=1). However, the fact that the Hazard Index value for Pb (0.459) which is a particularly toxic metal, was close to safe level, renders essential further investigation in order to provide more reliable characterizations of potential health risks.
Subject(s)
Cities , Dust/analysis , Metals, Heavy/analysis , Transportation , Calcium Carbonate/analysis , Environmental Monitoring , Greece , Humans , Quartz/analysis , Risk AssessmentABSTRACT
This study focuses on the effect of experimental parameters on the removal of ranitidine (RAN) during ozonation and the identification of the formed transformation products (TPs). The influence of pH value, the initial concentrations, the inorganic and the organic matter on RAN's removal were evaluated. Results indicated high reactivity of RAN with molecular aqueous ozone. Initial ozone concentration and pH were proven the major process parameters. Alkaline pH values promoted degradation and overall mineralization. Dissolved organic matter reacts competitively to RAN with the oxidants (ozone and/or radicals), influencing the target compound's removal. The presence of inorganic ions in the matrix did not seem to affect RAN ozonation. A total of eleven TPs were identified and structurally elucidated, with the complementary use of both Reversed Phase (RP) and Hydrophilic Interaction Liquid Chromatography (HILIC) quadrupole time of flight tandem mass spectrometry (Q-ToF-MS/MS). Most of the TPs (TP-304, TP-315b, TP-299b, TP-333, TP-283) were generated by the attack of ozone at the double bond or the adjacent secondary amine, with the abstraction of NO2 moiety, forming TPs with an aldehyde group and an imine bond. Oxidized derivatives with a carboxylic group (TP-315a, TP-331a, TP-331b, TP-299a) were also formed. RAN S-oxide was identified as an ozonation TP (TP-330) and its structure was confirmed through the analysis of a reference standard. TP-214 was also produced during ozonation, through the CN bond rupture adjacent to the NO2 moiety. HILIC was used complementary to RP, either for the separation and identification of TPs with isomeric structures that may have been co-eluted in RPLC or for the detection of new TPs that were not eluted in the RP chromatographic system. Retention time prediction was used as a supporting tool for the identification of TPs and results were in accordance with the experimental ones in both RP and HILIC.
Subject(s)
Models, Chemical , Ozone/chemistry , Ranitidine/chemistry , Water Pollutants, Chemical/chemistry , Oxidation-ReductionABSTRACT
This study focused on (a) the development of a screening methodology, in order to determine the main experimental variables affecting chlorinated and brominated disinfection by-product (DBP) formation in water during chlorination experiments and (b) the application of a central composite design (CCD) using response surface methodology (RSM) for the mathematical description and optimization of DBP formation. Chlorine dose and total organic carbon (TOC) were proven to be the main factors affecting the formation of total chlorinated DBPs, while chlorine dose and bromide concentration were the main parameters affecting the total brominated THMs. Longer contact time promoted a rise in chlorinated DBPs' concentration even in the presence of a minimal amount of organic matter. A maximum production of chlorinated DBPs was observed under a medium TOC value and it reduced at high TOC concentrations, possibly due to the competitive production of brominated THMs. The highest concentrations of chlorinated THMs were observed at chlorine dose 10 mg L(-1) and TOC 5.5 mg L(-1). The formation of brominated DBPs is possible even with a minimum amount of NaOCl in the presence of high concentration of bromide ions. Brominated DBPs were observed in maximum concentrations using 8 mg L(-1) of chlorine in the presence of 300 µg L(-1) bromides.
Subject(s)
Disinfectants/chemistry , Disinfection/methods , Trihalomethanes/chemistry , Water Pollutants, Chemical/chemistry , Water Purification/methods , Bromides/chemistry , Halogenation , Models, ChemicalABSTRACT
Exposure to ß-N-methylamino-l-alanine (BMAA) might be linked to the incidence of amyotrophic lateral sclerosis, Alzheimer's disease and Parkinson's disease. Analytical chemistry plays a crucial role in determining human BMAA exposure and the associated health risk, but the performance of various analytical methods currently employed is rarely compared. A CYANOCOST initiated workshop was organized aimed at training scientists in BMAA analysis, creating mutual understanding and paving the way towards interlaboratory comparison exercises. During this workshop, we tested different methods (extraction followed by derivatization and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analysis, or directly followed by LC-MS/MS analysis) for trueness and intermediate precision. We adapted three workup methods for the underivatized analysis of animal, brain and cyanobacterial samples. Based on recovery of the internal standard D3BMAA, the underivatized methods were accurate (mean recovery 80%) and precise (mean relative standard deviation 10%), except for the cyanobacterium Leptolyngbya. However, total BMAA concentrations in the positive controls (cycad seeds) showed higher variation (relative standard deviation 21%-32%), implying that D3BMAA was not a good indicator for the release of BMAA from bound forms. Significant losses occurred during workup for the derivatized method, resulting in low recovery (<10%). Most BMAA was found in a trichloroacetic acid soluble, bound form and we recommend including this fraction during analysis.