Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 19 de 19
Filter
Add more filters










Publication year range
1.
Bioresour Technol ; 399: 130559, 2024 May.
Article in English | MEDLINE | ID: mdl-38460566

ABSTRACT

Hydrothermal liquefaction (HTL) shows promise for converting wet biomass waste into biofuel, but the resulting high-strength process water (PW) requires treatment. This study explored enhancing energy recovery by anaerobic digestion using semi-batch reactors. Co-digesting manure with HTL-PW from wheat straw-manure co-HTL yielded methane (43-49% of the chemical oxygen demand, COD) at concentrations up to 17.8 gCOD·L-1, whereas HTL-PW from sewage sludge yielded methane (43% of the COD) up to only 12.8 gCOD·L-1 and complete inhibition occurred at 17 gCOD·L-1. Microbial community shifts confirmed inhibition of methanogenic archaea, while hydrolytic-fermentative bacteria were resilient. Differences in chemical composition, particularly higher levels of N-containing heterocyclic compounds in PW of sewage sludge, likely caused the microbial inhibition. The considerable potential of combining HTL with anaerobic digestion for enhanced energy recovery from straw-manure in an agricultural context is demonstrated, yet sewage sludge HTL-PW requires more advanced approaches to deal with methanogenesis inhibitors.


Subject(s)
Sewage , Wastewater , Sewage/microbiology , Triticum , Manure , Anaerobiosis , Bioreactors , Methane , Biofuels
2.
Mar Pollut Bull ; 199: 115919, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38134872

ABSTRACT

Marine oil spills have devastating environmental impacts and extrapolation of experimental fate and impact data from the lab to the field remains challenging due to the lack of comparable field data. In this work we compared two field systems used to study in situ oil depletion with emphasis on biodegradation and associated microbial communities. The systems were based on (i) oil impregnated clay beads and (ii) hydrophobic Fluortex adsorbents coated with thin oil films. The bacterial communities associated with the two systems displayed similar compositions of dominant bacterial taxa. Initial abundances of Oceanospirillales were observed in both systems with later emergences of Flavobacteriales, Alteromonadales and Rhodobacterales. Depletion of oil compounds was significantly faster in the Fluortex system and most likely related to the greater bioavailability of oil compounds as compared to the clay bead system.


Subject(s)
Gammaproteobacteria , Petroleum Pollution , Petroleum , Petroleum/metabolism , Clay , Seawater/chemistry , Biodegradation, Environmental , Bacteria/metabolism , Hydrocarbons/metabolism
3.
Appl Environ Microbiol ; 89(11): e0098723, 2023 11 29.
Article in English | MEDLINE | ID: mdl-37943057

ABSTRACT

IMPORTANCE: Increased ship traffic in the Arctic region raises the risk of oil spills. With an average sea depth of 1,000 m, there is a growing concern over the potential release of oil sinking in the form of marine oil snow into deep Arctic waters. At increasing depth, the oil-degrading community is exposed to increasing hydrostatic pressure, which can reduce microbial activity. However, microbes thriving in polar regions may adapt to low temperature by modulation of membrane fluidity, which is also a well-known adaptation to high hydrostatic pressure. At mild hydrostatic pressures up to 8-12 MPa, we did not observe an altered microbial activity or community composition, whereas comparable studies using deep-sea or sub-Arctic microbial communities with in situ temperatures of 4-5°C showed pressure-induced effects at 10-15 MPa. Our results suggest that the psychrophilic nature of the underwater microbial communities in the Arctic may be featured by specific traits that enhance their fitness at increasing hydrostatic pressure.


Subject(s)
Petroleum Pollution , Petroleum , Water Pollutants, Chemical , Hydrostatic Pressure , Arctic Regions , Biodegradation, Environmental , Seawater/microbiology , Bacteria , Hydrocarbons
4.
J Environ Manage ; 348: 119046, 2023 Dec 15.
Article in English | MEDLINE | ID: mdl-37832286

ABSTRACT

Sewage sludge management poses challenges due to its environmental impact, varying composition, and stringent regulatory requirements. In this scenario, hydrothermal liquefaction (HTL) is a promising technology for producing biofuel and extracting phosphorus from sewage sludge. However, the toxic nature of the resulting process water (HTL-PW) raises concerns about integrating HTL into conventional wastewater treatment processes. This study investigated the inhibitory effects of HTL-PW on the activity of the main microbial functions in conventional activated sludge. Upon recirculation of the HTL-PW from the excess sludge into the wastewater treatment plant, the level of COD in the influent is expected to increase by 157 mgO2⋅L-1, resulting in 44% nitrification inhibition (IC50 of 197 mg⋅L-1). However, sorption of inhibitory compounds on particles can reduce nitrification inhibition to 27% (IC50 of 253 mg⋅L-1). HTL-PW is a viable carbon source for denitrification, showing nearly as high denitrification rates as acetate and only 17% inhibition at 157 mgO2⋅L-1 COD. Under aerobic conditions, heterotrophic organic nitrogen and organic matter conversion remains unaffected up to 223 mgO2⋅L-1 COD, with COD removal higher than 94%. This study is the first to explore the full integration of HTL in wastewater treatment plants for biofuel production from the excess activated sludge. Potential nitrification inhibition is concerning, and further long-term studies are needed to fully investigate the impacts.


Subject(s)
Nitrification , Water Purification , Sewage , Biofuels , Magnesium Oxide , Water Purification/methods , Nitrogen , Bioreactors , Denitrification , Waste Disposal, Fluid/methods
5.
Chemosphere ; 344: 140344, 2023 Dec.
Article in English | MEDLINE | ID: mdl-37802482

ABSTRACT

Knowledge on the photocatalytic degradability of the emerging poly- and perfluorinated alkyl substances (PFAS) in water, specifically GenX, is limited. GenX has been detected globally in river water and is considered potentially more toxic than legacy PFAS. In this study, we compared the photocatalytic degradability of GenX with the legacy compounds perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) using Fe-zeolite photocatalysts. After 7 h of irradiation, GenX showed lower removal (79%) and defluorination (33%) as compared to PFOA (100% removal and 69% defluorination) and PFOS (100% removal and 51% defluorination). The quasi-first-order degradation rate of GenX (1.5 h1) was 12 and 1.2 times lower than PFOA (18.4 h-1) and PFOS (1.8 h-1), respectively. Additionally, PFOA's defluorination rate (0.9 h-1) was approximately 2.6 and 9 times higher than GenX (0.35 h-1) and PFOS (0.1 h-1), respectively. These outcomes correlate with GenX's lower hydrophobicity, leading to reduced adsorption (40%) compared to PFOA (99%) and PFOS (87%). Based on identified transformation products, we proposed a GenX degradation pathway, resulting in ultra-short-chain PFASs with a chain length of 2 and 3 carbon atoms, while PFOA and PFOS degraded stepwise, losing 1 carbon-fluorine bond at a time, leading to gradually shorter chain lengths (from 7 to 2 carbon atoms). In conclusion, GenX is more challenging to remove and degrade due to its lower adsorption on the photocatalyst, potential steric hindrance, and higher production of persistent ultra-short-chain transformation products through photocatalysis.


Subject(s)
Alkanesulfonic Acids , Fluorocarbons , Zeolites , Water , Caprylates , Carbon
6.
Water Res ; 245: 120599, 2023 Oct 15.
Article in English | MEDLINE | ID: mdl-37717325

ABSTRACT

Can biofilms enhance the rates of phosphorus removal in wastewater treatment? In order to narrow the scientific gap on the effect of biofilm thickness on the activity and microbial community of phosphorus-accumulating bacteria, this study investigated biofilms of 30 to 1000 µm thickness in a moving bed biofilm reactor. Measurements on 5 different biofilm carriers showed that biomass-specific phosphorus release and uptake rates increased as a function of biofilm thickness for biofilms thinner than about 110 µm but were lower for thicker biofilms of about 550-1000 µm. The reduced phosphorus uptake and release rates in the thickest biofilms can result from substrate mass transfer limitations whereas the low activity in the thinnest biofilms can be related to a too high turnover rate in the biofilm due to heterotrophic growth. Additionally, the microbial ecology of the different biofilms confirms the observed phosphorus uptake and release rates. The results from the full-length 16S rRNA gene sequencing of the bacterial community showed that the thicker biofilms were characterized by higher relative abundance (40-58%) of potential phosphorus accumulating genera Zoogloea, Acinetobacter, Dechloromonas and Ca. Accumulibacter. In contrast, the thinner biofilms were dominated by the genus Ferribacterium (34-60%), which might be competing with phosphorus-accumulating bacteria as indicated by the relatively high acetate uptake rates in the thinner biofilms. It is concluded that there is an optimal biofilm thickness of 100-500 µm, at which the phosphorus accumulating bacteria have the highest activity.

7.
J Hazard Mater ; 446: 130656, 2023 03 15.
Article in English | MEDLINE | ID: mdl-36603421

ABSTRACT

Oil spill attenuation in Arctic marine environments depends on oil-degrading bacteria. However, the seasonally harsh conditions in the Arctic such as nutrient limitations and sub-zero temperatures limit the activity even for bacteria capable of hydrocarbon metabolism at low temperatures. Here, we investigated whether the variance between epipelagic (seasonal temperature and inorganic nutrient variations) and mesopelagic zone (stable environmental conditions) could limit the growth of oil-degrading bacteria and lead to lower oil biodegradation rates in the epipelagic than in the mesopelagic zone. Therefore, we deployed absorbents coated with three oil types in a SW-Greenland fjord system at 10-20 m (epipelagic) and 615-650 m (mesopelagic) water depth for one year. During this period we monitored the development and succession of the bacterial biofilms colonizing the oil films by 16S rRNA gene amplicon quantification and sequencing, and the progression of oil biodegradation by gas chromatography - mass spectrometry oil fingerprinting analysis. The removal of hydrocarbons was significantly different, with several polycyclic aromatic hydrocarbons showing longer half-life times in the epipelagic than in the mesopelagic zone. Bacterial community composition and density (16S rRNA genes/ cm2) significantly differed between the two zones, with total bacteria reaching to log-fold higher densities (16S rRNA genes/cm2) in the mesopelagic than epipelagic oil-coated absorbents. Consequently, the environmental conditions in the epipelagic zone limited oil biodegradation performance by limiting bacterial growth.


Subject(s)
Petroleum Pollution , Petroleum , Estuaries , RNA, Ribosomal, 16S/genetics , RNA, Ribosomal, 16S/metabolism , Seawater/microbiology , Hydrocarbons/metabolism , Bacteria/genetics , Bacteria/metabolism , Biodegradation, Environmental , Petroleum/metabolism
8.
Chemosphere ; 286(Pt 3): 131751, 2022 Jan.
Article in English | MEDLINE | ID: mdl-34399257

ABSTRACT

Oil spills in Arctic marine environments are expected to increase concurrently with the expansion of shipping routes and petroleum exploitation into previously inaccessible ice-dominated regions. Most research on oil biodegradation focusses on the bulk oil, but the fate of the water-accommodated fraction (WAF), mainly composed of toxic aromatic compounds, is largely underexplored. To evaluate the bacterial degradation capacity of such dissolved aromatics in Greenlandic seawater, microcosms consisting of 0 °C seawater polluted with WAF were investigated over a 3-month period. With a half-life (t1/2) of 26 days, m-xylene was the fastest degraded compound, as measured by gas chromatography - mass spectrometry. Substantial slower degradation was observed for ethylbenzene, naphthalenes, phenanthrene, acenaphthylene, acenaphthene and fluorenes with t1/2 of 40-105 days. Colwellia, identified by 16S rRNA gene sequencing, was the main potential degrader of m-xylene. This genus occupied up to 47 % of the bacterial community until day 10 in the microcosms. Cycloclasticus and Zhongshania aliphaticivorans, potentially utilizing one-to three-ringed aromatics, replaced Colwellia between day 10 and 96 and occupied up to 6 % and 23 % of the community, respectively. Although most of the WAF can ultimately be eliminated in microcosms, our results suggest that the restoration of an oil-impacted Arctic environment may be slow as most analysed compounds had t1/2 of over 2-3 months and the detrimental effects of a spill towards the marine ecosystem likely persist during this time.


Subject(s)
Petroleum Pollution , Petroleum , Water Pollutants, Chemical , Arctic Regions , Biodegradation, Environmental , Ecosystem , Gammaproteobacteria , Hydrocarbons , Petroleum Pollution/analysis , RNA, Ribosomal, 16S/genetics , Seawater , Water , Water Pollutants, Chemical/analysis
9.
Environ Sci Technol ; 53(21): 12197-12206, 2019 Nov 05.
Article in English | MEDLINE | ID: mdl-31566367

ABSTRACT

Increased economic activity in the Arctic may increase the risk of oil spills. Yet, little is known about the degradation of oil spills by solar radiation and the impact of nutrient limitation on oil biodegradation under Arctic conditions. We deployed adsorbents coated with thin oil films for up to 4 months in a fjord in SW Greenland to simulate and investigate in situ biodegradation and photo-oxidation of dispersed oil droplets. Oil compound depletion by dissolution, biodegradation, and photo-oxidation was untangled by gas chromatography-mass spectrometry-based oil fingerprinting. Biodegradation was limited by low nutrient concentrations, reaching 97% removal of nC13-26-alkanes only after 112 days. Sequencing of bacterial DNA showed the slow development of a bacterial biofilm on the oil films predominated by the known oil degrading bacteria Oleispira, Alkanindiges and Cycloclasticus. These taxa could be related to biodegradation of shorter-chain (≤C26) alkanes, longer-chain (≥C16) and branched alkanes, and polycyclic aromatic compounds (PACs), respectively. The combination of biodegradation, dissolution, and photo-oxidation depleted most PACs at substantially faster rates than the biodegradation of alkanes. In Arctic fjords during summer, nutrient limitation may severely delay oil biodegradation, but in the photic zone, photolytic transformation of PACs may play an important role.


Subject(s)
Petroleum Pollution , Petroleum , Water Pollutants, Chemical , Alkanes , Arctic Regions , Biodegradation, Environmental , Estuaries , Greenland , Seawater , Solubility
10.
Water Res ; 148: 459-468, 2019 01 01.
Article in English | MEDLINE | ID: mdl-30408732

ABSTRACT

In pristine sea ice-covered Arctic waters the potential of natural attenuation of oil spills has yet to be uncovered, but increasing shipping and oil exploitation may bring along unprecedented risks of oil spills. We deployed adsorbents coated with thin oil films for up to 2.5 month in ice-covered seawater and sea ice in Godthaab Fjord, SW Greenland, to simulate and investigate in situ biodegradation and photooxidation of dispersed oil. GC-MS-based chemometric methods for oil fingerprinting were used to identify characteristic signatures for dissolution, biodegradation and photooxidation. In sub-zero temperature seawater, fast degradation of n-alkanes was observed with estimated half-life times of ∼7 days. PCR amplicon sequencing and qPCR quantification of bacterial genes showed that a biofilm with a diverse microbial community colonised the oil films, yet a population related to the psychrophilic hydrocarbonoclastic gammaproteobacterium Oleispira antarctica seemed to play a key role in n-alkane degradation. Although Oleispira populations were also present in sea ice, we found that biofilms in sea ice had 25 to 100 times lower bacterial densities than in seawater, which explained the non-detectable n-alkane degradation in sea ice. Fingerprinting revealed that photooxidation, but not biodegradation, transformed polycyclic aromatic compounds through 50 cm-thick sea ice and in the upper water column with removal rates up to ∼1% per day. Overall, our results showed a fast biodegradation of n-alkanes in sea ice-covered seawater, but suggested that oils spills will expose the Arctic ecosystem to bio-recalcitrant PACs over prolonged periods of time.


Subject(s)
Petroleum Pollution , Petroleum , Water Pollutants, Chemical , Arctic Regions , Biodegradation, Environmental , Greenland , Ice Cover , Seawater , Solubility
11.
Sci Total Environ ; 626: 1243-1258, 2018 Jun 01.
Article in English | MEDLINE | ID: mdl-29898532

ABSTRACT

New economic developments in the Arctic, such as shipping and oil exploitation, bring along unprecedented risks of marine oil spills. Microorganisms have played a central role in degrading and reducing the impact of the spilled oil during past oil disasters. However, in the Arctic, and in particular in its pristine areas, the self-cleaning capacity and biodegradation potential of the natural microbial communities have yet to be uncovered. This review compiles and investigates the current knowledge with respect to environmental parameters and biochemical constraints that control oil biodegradation in the Arctic. Hereby, seawaters off Greenland are considered as a case study. Key factors for biodegradation include the bioavailability of hydrocarbons, the presence of hydrocarbon-degrading bacteria and the availability of nutrients. We show how these key factors may be influenced by the physical oceanographic conditions in seawaters off Greenland and other environmental parameters including low temperature, sea ice, sunlight regime, suspended sediment plumes and phytoplankton blooms that characterize the Arctic. Based on the acquired insights, a first qualitative assessment of the biodegradation potential in seawaters off Greenland is presented. In addition to the most apparent Arctic characteristics, such as low temperature and sea ice, the impact of typical Arctic features such as the oligotrophic environment, poor microbial adaptation to hydrocarbon degradation, mixing of stratified water masses, and massive phytoplankton blooms and suspended sediment plumes merit to be topics of future investigation.


Subject(s)
Biodegradation, Environmental , Petroleum Pollution/analysis , Water Pollutants, Chemical/analysis , Arctic Regions , Bacteria/metabolism , Greenland , Ice Cover/microbiology , Petroleum/metabolism , Seawater/chemistry , Seawater/microbiology , Water Pollutants, Chemical/metabolism
12.
Sci Total Environ ; 637-638: 336-348, 2018 Oct 01.
Article in English | MEDLINE | ID: mdl-29751313

ABSTRACT

Although there is increased global environmental concern about emerging organic micropollutants (EOMPs) such as pharmaceuticals, personal care products (PPCPs) and polar pesticides, limited information is available on their occurrence in Africa. This study presents unique data on concentrations and loads of 31 PPCPs and 10 pesticides in four wastewater stabilization ponds (WSPs) and receiving rivers (flowing through urban centres) in Kenya. The WSPs indicate a high potential to remove pharmaceutically active compounds (PhACs) with removals by up to >4 orders of magnitude (>99.99% removal), mainly occurring at the facultative stage. However, there are large differences in removal among the different classes, and a shift in the relative PhACs occurrence is observed during wastewater treatment. Whereas the influent is dominated by high-consumption PhACs like anti-inflammatory drugs (e.g. paracetamol and ibuprofen, up to 1000 µg L-1), the most recalcitrant PhACs including mainly antibiotics (e.g. sulfadoxin and sulfamethoxazole) and antiretrovirals (e.g. lamivudine and nevirapine) are largely abundant (up to 100 µg L-1) in treated effluent. Overall, concentrations of EOMPs in the Nzoia Basin rivers are the highest in dry season (except pesticides) and in small tributaries. They are of the same order of magnitude as those measured in the western world, but clearly lower than what we recently measured in the Ngong River, Nairobi region. Based on the specific consumption patterns and recalcitrant behavior, high concentrations (>1000 ng L-1) are observed in the rivers for PPCPs like lamivudine, zidovudine, sulfamethoxazole and methylparaben. Concentration levels of pesticides are in general one order of magnitude lower (<250 ng L-1). Our data suggest a continuous input of EOMPs to the rivers from both point (WSPs) and diffuse (urban centres) sources. To better understand and manage the impact of both sources, EOMP removal mechanisms in WSPs and their attenuation in rivers merit further research.


Subject(s)
Cosmetics/analysis , Environmental Monitoring , Pesticides/analysis , Pharmaceutical Preparations/analysis , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/analysis , Kenya , Ponds , Rivers , Wastewater/chemistry , Wastewater/statistics & numerical data
13.
J Hazard Mater ; 353: 127-134, 2018 07 05.
Article in English | MEDLINE | ID: mdl-29660698

ABSTRACT

The risk of oil spills in cold marine environments is expected to increase in response to trans-Arctic shipping and as Arctic oil reserves get exploited. Marine hydrocarbon-degrading microbes can reduce the impact of spilled hydrocarbons, but their degradation capabilities at low temperature are yet to be uncovered. We combined DNA amplicon sequencing and chemometrics to investigate the effect of decreasing temperature (0-15 °C) on the succession and function of hydrocarbon-degrading bacteria in seawater. The bacterial community and degradation patterns were investigated at time points when a similar amount of hydrocarbons was mineralised at the different temperatures. This allowed decomposing the effect of temperature into a main component related to the reduced microbial activity at low temperature and a secondary effect. The reduced microbial activity at low temperature delayed the microbial community succession and degradation rates. The secondary effect of temperature was most pronounced at 0 °C, where (1) degradation of the least water-soluble n-alkanes (>C12) was suppressed in contrast to a relative stronger degradation of the most water-soluble n-alkanes (

Subject(s)
Hydrocarbons/metabolism , Microbiota , Seawater/microbiology , Temperature , Water Pollutants, Chemical/metabolism , Bacteria/genetics , Bacteria/metabolism , Biodegradation, Environmental , RNA, Ribosomal, 16S/genetics
14.
J Hazard Mater ; 323(Pt A): 2-10, 2017 Feb 05.
Article in English | MEDLINE | ID: mdl-27339948

ABSTRACT

This research addresses some critical challenges regarding the validation of a quantitative multi-residue method for pharmaceuticals in wastewater making use of modern SPE-LC-Orbitrap high-resolution mass spectrometry. Particular attention is given to study in detail response linearity, to realistically estimate detection limits, and to express the measurement precision of the analyte concentration, obtained by external calibration. First, linearity of the Orbitrap response showed to be matrix dependent in a counter intuitive way: stronger deviations from linearity were observed for pure solvent standards than for complex matrices like wastewater. Second, detection limits risk to be overestimated for ubiquitously present compounds for which true blank matrix samples are hard to find, leading to false negative findings. A novel and easy applicable methodology is presented to allow a better estimation of detection limits using the response of the natural isotopes. Third, a statistical methodology to estimate the measurement precision of the analyte concentration using basic validation parameters is developed specifically for the context of multi-residue quantification.


Subject(s)
Chromatography, High Pressure Liquid/statistics & numerical data , Mass Spectrometry/statistics & numerical data , Pharmaceutical Preparations/analysis , Solid Phase Extraction/statistics & numerical data , Wastewater/analysis , Water Pollutants, Chemical/analysis , Limit of Detection , Linear Models , Reproducibility of Results , Uncertainty
15.
Anal Chem ; 87(4): 2170-7, 2015 Feb 17.
Article in English | MEDLINE | ID: mdl-25565253

ABSTRACT

Modern high-resolution mass spectrometry (HRMS) enables full-spectrum trace level analysis of emerging environmental organic contaminants. This raises the opportunity for post-acquisition suspect screening when no reference standards are a priori available. When setting up a conventional screening identification train based on successively different identification criteria including mass error and isotope fit, the false negative rate typically accumulates upon advancing through the decision tree. The challenge is thus to elaborate a well-balanced screening, in which the different criteria are equally stringent, leading to a controllable number of false negatives. Presented is a novel suspect screening approach using liquid-chromatography Orbitrap HRMS. Based on a multivariate statistical model, the screening takes into account the accurate mass error of the mono isotopic ion and up to three isotopes, isotope ratios, and a peak/noise filter. As such, for the first time, controlling the overall false negative rate of the screening algorithm to a desired level (5% in this study) is achieved. Simultaneously, a well-balanced identification decision is guaranteed taking the different identification criteria as a whole in a holistic statistical approach. Taking into account 1, 2, and 3 isotopes decreases the false positive rate from 22, 2.8 to <0.3%, but the cost of increasing the median limits of identification from 200, 2000 to 2062 ng L(-1), respectively, should also be considered. As proof of concept, 7 biologically treated wastewaters were screened toward 77 suspect pharmaceuticals resulting in the indicative identification of 25 suspects. Subsequently obtained reference standards allowed confirmation for 19 out of these 25 pharmaceutical contaminants.


Subject(s)
Mass Spectrometry/methods , Pharmaceutical Preparations/analysis , Wastewater/analysis , Water Pollutants, Chemical/analysis , Chromatography, Liquid/methods , Multivariate Analysis
16.
Chemosphere ; 119 Suppl: S2-8, 2015 Jan.
Article in English | MEDLINE | ID: mdl-24751143

ABSTRACT

Through systematic research a novel analytical method using solid-phase extraction (SPE) and liquid chromatography magnetic sector mass spectrometry was developed for the measurement of 43 pharmaceuticals in wastewater. A thorough method validation quantified the contribution of both the extraction recovery and matrix effects in the overall method process efficiency, and a detailed uncertainty analysis was performed to elaborate a quality labelling strategy to be used in data interpretation. Compounds for which a precise (relative standard deviation<20%) process efficiency between 60% and 140% was determined, were labelled as 'quantitative' whereas the results for other compounds should be interpreted as 'indicative'. Method application on influent and effluent samples of (i) a conventional active sludge system and (ii) a parallel membrane bioreactor/conventional active sludge wastewater treatment plant in Belgium revealed the occurrence of 22 pharmaceuticals. The anti-inflammatory drug diclofenac and the antidepressant venlafaxine were measured in the effluents at concentrations ranging from 0.5 to 1.8 µg L(-1) and 0.2 to 0.5 µg L(-1), respectively, which indicated to be of high potential environmental risk for the receiving river Dender, Belgium.


Subject(s)
Mass Spectrometry/methods , Pharmaceutical Preparations/analysis , Wastewater/analysis , Water Pollutants, Chemical/analysis , Belgium , Bioreactors , Chromatography, Liquid/methods , Environmental Monitoring , Magnetic Phenomena , Reproducibility of Results , Sewage , Solid Phase Extraction/methods , Waste Disposal, Fluid
17.
Anal Bioanal Chem ; 406(11): 2533-47, 2014 Apr.
Article in English | MEDLINE | ID: mdl-24633561

ABSTRACT

The ever-growing number of emerging micropollutants such as pharmaceuticals requests rapid and sensitive full-spectrum analytical techniques. Time-of-flight high-resolution mass spectrometry (TOF-HRMS) is a promising alternative for the state-of-the-art tandem mass spectrometry instruments because of its ability to simultaneously screen for a virtually unlimited number of suspect analytes and to perform target quantification. The challenge for such suspect screening is to develop a strategy, which minimizes the false-negative rate without restraining numerous false-positives. At the same time, omitting laborious sample enrichment through large-volume injection ultra-performance liquid chromatography (LVI-UPLC) avoids selective preconcentration. A suspect screening strategy was developed using LVI-UPLC-TOF-MS aiming the detection of 69 multi-class pharmaceuticals in surface water without the a priori availability of analytical standards. As a novel approach, the screening takes into account the signal-intensity-dependent accurate mass error of TOF-MS, hereby restraining 95 % of the measured suspect pharmaceuticals present in surface water. Application on five Belgian river water samples showed the potential of the suspect screening approach, as exemplified by a false-positive rate not higher than 15 % and given that 30 out of 37 restrained suspect compounds were confirmed by the retention time of analytical standards. Subsequently, this paper discusses the validation and applicability of the LVI-UPLC full-spectrum HRMS method for target quantification of the 69 pharmaceuticals in surface water. Analysis of five Belgian river water samples revealed the occurrence of 17 pharmaceuticals in a concentration range of 17 ng L(-1) up to 3.1 µg L(-1).


Subject(s)
Chromatography, Liquid/methods , Mass Spectrometry/methods , Pharmaceutical Preparations/analysis , Rivers/chemistry , Water Pollutants, Chemical/analysis , Chromatography, Liquid/instrumentation
18.
Anal Chim Acta ; 789: 74-82, 2013 Jul 30.
Article in English | MEDLINE | ID: mdl-23856232

ABSTRACT

Uniform guidelines for the data processing and validation of qualitative and quantitative multi-residue analysis using full-spectrum high-resolution mass spectrometry are scarce. Through systematic research, optimal mass accuracy and sensitivity are obtained after refining the post-processing of the HRMS data. For qualitative analysis, transforming the raw profile spectra to centroid spectra is recommended resulting in a 2.3 fold improved precision on the accurate mass determination of spectrum peaks. However, processing centroid data for quantitative purposes could lead to signal interruption when too narrow mass windows are applied for the construction of extracted ion chromatograms. Therefore, peak integration on the raw profile data is recommended. An optimal width of the mass window of 50 ppm, which is a trade-off between sensitivity and selectivity, was obtained for a TOF instrument providing a resolving power of 20,000 at full width at half maximum (FWHM). For the validation of HRMS analytical methods, widespread concepts such as the signal-to-noise ratios for the determination of decision limits and detection capabilities have shown to be not always applicable because in some cases almost no noise can be detected anymore. A statistical methodology providing a reliable alternative is extended and applied.


Subject(s)
Algorithms , Chromatography, Liquid/methods , Mass Spectrometry/methods , Limit of Detection , Molecular Weight , Pharmaceutical Preparations/analysis , Reproducibility of Results , Sensitivity and Specificity , Signal-To-Noise Ratio , Spectrometry, Mass, Electrospray Ionization/methods , Water Pollutants, Chemical/analysis
19.
Sci Total Environ ; 437: 153-64, 2012 Oct 15.
Article in English | MEDLINE | ID: mdl-22935682

ABSTRACT

This paper presents the development and application of a new multi-residue analytical method providing the first data on the environmental occurrence of human pharmaceuticals in Africa, particularly the Nairobi River basin (Kenya). Based on pharmaceutical consumption data available for the Nairobi region, 43 'priority' pharmaceutically active ingredients (PAIs) were selected for this study. On the basis of magnetic sector high-resolution mass spectrometry, a new methodology involving both full-scan screening and selective target analysis has been developed to investigate the presence of the defined priority PAIs. Subsequent analysis of the corresponding standard compounds provided the full confirmation and indicative concentrations (low ng/L-high µg/L) of 10 human PAIs in the Nairobi River. The detected compounds belong to different classes, i.e. antibiotics, analgesic/anti-inflammatory and anti-epileptic drugs, antimalarials and antiretrovirals. Ibuprofen, paracetamol, sulfamethoxazole and zidovudine showed to be the most concentrated PAIs (about 10-30 µg/L). The concentration of the antiretrovirals (lamivudine, zidovudine and nevirapine) is clearly higher than those reported in the literature, although environmental data on this class of PAIs are still very limited. To the best of our knowledge, this is the first study that provides evidence of detection of lamivudine in surface water. The presented unique data on the occurrence of selected PAIs in the aquatic environment of Africa clearly show that the high prevalence of specific diseases like HIV/AIDS infection in developing countries might result in a different pattern of PAIs in environmental waters compared to the more developed regions.


Subject(s)
Drug Residues/analysis , Mass Spectrometry/methods , Rivers/chemistry , Water Pollutants, Chemical/analysis , Environmental Monitoring/methods , Humans , Kenya
SELECTION OF CITATIONS
SEARCH DETAIL
...