•A QuEChERS methodology is applied in the lipophilic marine biotoxins (MBTXs) analysis.•UHPLC with HRMS/MS furnishes excellent results in the quantitative analysis of MBTXs.•Calibration with ...surrogate matrix matched standards provides reliable results.•Eprinomectin is proposed as internal standard for lipophilic marine biotoxins.•The method is suitable for the analysis of both fresh and canned bivalve molluscs.
A new method for the analysis of lipophilic marine biotoxins (okadaic acid, dinophysistoxins, azaspiracids, pectenotoxins, yessotoxins, spirolids) in fresh and canned bivalves has been developed. A QuEChERS methodology is applied; i.e. the analytes are extracted with acetonitrile and clean-up of the extracts is performed by dispersive solid phase extraction with C18. The extracts are analyzed by ultra-high performance liquid chromatography coupled to a hybrid quadrupole-Orbitrap mass spectrometer, operating in tandem mass spectrometry mode, with resolution set at 70,000 (m/z 200, FWHM). Separation of the analytes, which takes about 10min, is carried out in gradient elution mode with a BEH C18 column and mobile phases based on 6.7mM ammonia aqueous solution and acetonitrile mixtures. For each analyte the molecular ion and 1 or 2 product ions are acquired, with a mass accuracy better than 5ppm. The quantification is performed using surrogate matrix matched standards, with eprinomectin as internal standard. The high-throughput method, which has been successfully validated, fulfills the requirements of European Union legislation, and has been implemented as a routine method in a public health laboratory.
► Levels of POPs in fishing grounds of the NW Mediterranean are considered as baseline. ► Biliary FACs reflect a higher PAH exposure in the Northern station. ► Both sole fish can be equally adequate ...for pollution monitoring. ► Immune non-specific parameters respond to PAH exposure.
Sediment polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorinated pesticides (OCls) and polybrominated diphenyl ethers (PBDEs) were measured during winter 2011 at seven sites on the Catalan coast (NW Mediterranean). Also at these sites, the benthic fish Solea solea and Solea senegalensis were fished for biomarker analysis. Chemical concentrations did not exceed the values considered safe by sediment quality guidelines (SQGs) for PAHs. However, levels of DDT (94.5ng/g d.w.) and PCBs (15.1ng/g d.w.) were significant in the Ebre Delta. Nonspecific immune parameters in S. solea showed a positive correlation between lysozyme activity in plasma and PAH content in sediment (r=0.982, p<0.01) and the opposite trend occurred with the complement test (ACH50) (r=−0.837; p<0.05). Cell counts (monocytes, lymphocytes and granulocytes) were elevated at most PAH-affected sites. A high concentration of bile FACs (fluorescent aromatic compounds) occurred at the northern station.
A comprehensive characterization of five of the seven priority organic pollutants listed in the draft of the “Working document on sludge” EU, 2000. Working Document on Sludge 3rd Draft. Unpublished, ...19 p has been carried out during 2001–2003 in sludge samples from Catalonia (NE Spain). One hundred and thirty-nine samples belonging to 20 Waste Water Treatment Plants (WWTPs), seven sludge treatment (thermal drying) and three composting sludge plants were taken in order to determine the concentration of polychlorinated dibenzo-
p-dioxins and -furans (PCDD/Fs), di-2-(ethyl-hexyl)-phthalate (DEHP), nonylphenol and nonylphenol ethoxylates with one or two ethoxy groups (NPE), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs).
PCDD/F concentrations were in general lower than the 100
ng I-TEQ/kg limit suggested in the above-mentioned document. In the same way, 98.5% for PCBs, 97% for PAH and 92.8% for DEHP of the samples presented concentrations lower than 0.8
mg/kg
dm, 6
mg/kg
dm and 100
mg/kg
dm, respectively.
In contrast, the vast majority of samples contained NPE concentrations much higher than 50
mg/kg
dm limit. The values ranged from 14.3 to 3150
mg/kg
dm (median value
=
286.6
mg/kg) being composted sludge samples the less contaminated ones (17.9–363.4
mg/kg
dm; median value
=
89.3
mg/kg). Special attention should be paid to the Catalan sludge NPE contamination owing to the high levels detected.
Simultaneous distillation extraction (SDE) and closed-loop stripping analysis (CLSA) show great capacity for organic compound extraction. Here we used these techniques to obtain and characterize a ...wide range of volatile compounds from aged cava sparkling wine. We also explored the potential application of head space-solid phase micro extraction (HS-SPME) to determine the distinctive volatile compounds of aged cava as this technique is a common extraction method in quality flavour control. For SDE, 50
mL of cava were extracted with pentane/dichloromethane during 4
h in a Likens–Nickerson (LN) extraction apparatus; while for CLSA, 25
mL of cava were stirred during 1
h into a CLSA apparatus with an adsorbent trap of granulated activated carbon. HS-SPME was performed at 35
°C using 2
ml of sample for 30
min. The 20-mm SPME fibber was coated with a 50/30-μm layer of divinylbenzene–carboxen–polydimethylsiloxane (DVB–CAR–PDMS). All the extraction methods were followed by gas chromatography–mass spectrometry (GC–MS) analysis. SDE and CLSA allowed the identification of 84 volatile compounds. Almost 40% of the volatiles from these two techniques were obtained by HS-SPME. Moreover, here we provide the first description of several tentatively identified compounds such as lilial, octanal, 2-octanone, isopropyl disulfide, methylthiophen-3-one, α-amyl-cinnamaldehyde, ethyl 2-furancarboxylate, 2-acetylfuran, and 5-methylfurfural in cava.
Interest in identifying pools of antibacterial-resistance genes has grown over the last decade, with veterinary antibiotics (VAs) receiving particular attention. In this paper, a mesoscale study ...aimed at evaluating the vertical transport of common VAs—namely, fluoroquinolones, tetracyclines, sulfonamides, and lincosamides in agricultural soil subjected to drip irrigation—was performed under greenhouse conditions. Accordingly, leachates of cropped and uncropped soil, amended with swine-slurry leading to 19–38 μg kg
−1
(dry mass) antibiotics in the soil, were analyzed over the course of the productive cycle of a lettuce (42 days) with three sampling campaigns (
N
= 24). High lincomycin (LCM) concentrations (30–39 μg L
−1
) were detected in the leachates collected from the swine-slurry-amended soil. The highest LCM mass recovered in the leachates (30.1 ± 1.63 %) was obtained from cropped experimental units. In addition, the LCM leaching constant and its leaching potential as obtained from the first-order model were higher in the leachates from the cropped experimental units. Lower concentrations of sulfadimethoxine were also detected in leachates and in soil. Enrofloxacin and oxytetracycline occurred only in soil, which is consistent with high soil interaction.
The aim of this work is to give representative data on polychlorinated dibenzo-
p-dioxins (PCDD), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyl (PCBs) from stack gas emissions of ...an urban solid waste management plant which has to comply with the limit of 0.1
ng I-TEQ/N
m
3. In particular, the study is focused on 29 target compounds, the seventeen 2,3,7,8-PCDDs/Fs, four non-
ortho PCBs and eight mono-
ortho PCBs which configure so-called ‘
dioxin-like’ PCBs (DL-PCBs). To this end, emission measurements were performed during one year over the three operating combustion lines in a selected waste management plant. In general, accurate methodology allowed characterizing all target compounds in almost all the samples analyzed. In addition, a typical pattern for DL-PCBs is reported. The pattern presented PCB #118 to be the highest, nevertheless the figures demonstrated DL-PCBs contribution to the total TEQ around 3% being PCB #126 the most important congener due to its TEF of 0.1. Finally, remarkable differences were achieved in comparison with both environmental and biological samples such as soils, sediments, human milk or fish since these matrices may present DL-PCB contribution to the total TEQ up to 77%.
Polyethoxylated alkylphenols (AP
nEO, where
n is the number of ethylene oxide molecules), are non-ionic surfactants widely used for domestic and industrial purposes. Most of AP
nEO are ...polyethoxylated nonylphenols (NP
nEO). NP
nEO are widespread environmental pollutants with relatively low toxicity for mammals and higher toxicity for aquatic organisms. In addition, they have been described as endocrine disrupters in recent publications.
One of the main problems related to these surfactants is their uncomplete degradation, even in the most effective sewage treatment plants. Usually, the final products, more toxic and resistant to biological degradation than NP
nEO, are nonylphenol (NP), monoethoxylated nonylphenol (NP1EO), diethoxylated nonylphenol (NP2EO), nonylphenoxy acetic acid (NP1EC), and nonylphenoxyethoxy acetic acid (NP2EC).
In this paper, the degradation of NP
nEO was studied in the different processes of a sewage treatment plant. For this purpose, NP, NP1EO and NP2EO were analysed in composite samples collected at different points along the plant (influent, pre-treatment effluent, primary effluent, plant effluent).
Analyses were carried out by isotopic dilution-HRGC/MS, using available labelled nonylphenols (
13C
6-NP,
13C
6-NP1EO,
13C
6-NP2EO) as internal standards. Extraction of NP
nEO from aqueous samples, previous to analysis, was performed by the Likens-Nickerson method (simultaneous steam distillation/solvent extraction, SDE).
Eight sewage sludges from rural, urban and industrial wastewater treatment plants (WWTPs) in Catalonia (Spain) were analysed for polychlorinated dibenzo-
p-dioxins (PCDDs), dibenzofurans (PCDFs) and ...biphenyls (PCBs) to determine the present levels of contamination. A method based on an automated cleanup system followed by an isotope-dilution high-resolution mass spectrometric analysis was employed. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors (WHO-TEFs) proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. The WHO-TEQ
PCDD/F values for these samples ranged from 4.9 to 20.8 pg/g dry weight (d.w.), with a mean value of 9.3 pg/g d.w., whereas WHO-TEQ
PCB levels ranged between 1.9 and 6.6 pg/g d.w., with a mean value of 4.2 pg/g d.w. The WHO-TEQ
PCB contribution varied from 13% to 50%, suggesting that PCB contribution on the toxicity of the samples must be taken into account. Moreover, these contemporary PCDD, PCDF and PCB concentrations were compared with previous data obtained from sewage sludge samples collected during the 80s. Our findings show that contemporary PCDD, PCDF and PCB levels have declined since the 80s.
The amount of sewage sludge generated in Europe is expected to surpass the 10 million tons/year in 2006 as a result of the waste water treatment process according to the Water Policy in European ...Union. Sewage sludge is what is left behind after water is cleaned in waste treatment plants and is characterized for this high content in nitrogen and phosphorous that could be of great importance in agriculture as fertilizer or soil conditioner. On the other hand, pollutants like metals and organic contaminants are usually removed from water and are accumulated in the sewage sludge, reaching the food chain if their concentrations are not below the safe limits established by the European legislation. The latter issue is of great concern nowadays and in this sense, different works alert against the use of the sewage sludge in agriculture arguing that serious illnesses, even resulting in death as well as adverse environmental impacts are associated to the application of sewage sludge.
This work is a continuation of a former comprehensive survey on of priority organic pollutant in sludges for agricultural purposes carried out by our group in Catalonia and this time is focused on the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), one of the most toxic group of organic compounds listed in the Work Document on Sludge which is the reference tool in this field in Europe and is also included in the Stockholm Convention. Eighty eight samples were collected from the end of 2003 to April 2006 and the concentrations detected were lower than the 100 ng/kg I-TEQ limit recommended by the European legislation (EC, 2000). Thus, sewage sludges generated in Catalonia do not represent a threat to human health if they are used as fertilizers in agriculture.
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