Multicriteria optimisation of a simultaneous supercritical fluid extraction and clean-up procedure for the determination of persistent organohalogenated pollutants in aquaculture samples

A useful tool based on a single-step extraction and clean-up procedure for the determination of 15 organohalogenated pollutants (including brominated flame retardants) in aquaculture samples, using aluminium oxide basic and acidic silica gel in the supercritical extraction cell followed by gas chromatography with electron capture detection or mass spectrometry has been developed. This effective clean-up step ensures a minimum of chromatographic difficulties related to complex matrix components such as aquaculture feed. The extraction procedure has been screened by a fractional factorial design for the preliminary statistically significant parameters. The factors selected were extraction temperature, pressure, static extraction time, dynamic extraction time and carbon dioxide flow rate. The Doehlert design, followed by a multicriteria decision-making strategy, was then performed in order to determine the optimum conditions for the two most significant factors: pressure (165 bar) and dynamic extraction time (27 min). Under optimal conditions, the procedure developed with GC-MS/MS provides an excellent linearity, detection (0.01-0.2 ng g(-1)) and quantification limits (0.05-0.8 ng g(-1)) for most of the analytes investigated. The feasibility of the proposed supercritical fluid extraction method was validated by analysing two reference materials and fish feed and shellfish samples with satisfactory results.     

Investigations of chemical fraction of Co and Ni in industrial fly ash and mobility of metals in environmental conditions

The quantitative evaluation of chemical fraction of Co and Ni in the industrial fly ash by methods of five step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH=7), (ii) acid-soluble (pH=5), (iii) oxide, (iv) sulfide and (v) residue metal fractions. It was discovered, that the total extraction of the studied metals from fly ash to solutions take place in the following quantities Co - 35.5 and Ni - 153.0mgkg(-1). The investigations of chemical fractions proved that the subject metals occur mainly in fly ash as: oxide (Co - 7.0, Ni - 28.5mgkg(-1)) and residue (Co - 11.5, Ni - 42.5mgkg(-1)) as well as sulfide (Co - 8.5, Ni - 46.5mgkg(-1)). Low concentrations of metals for water-soluble fraction (Co - 0.7, Ni - 1.2mgkg(-1)) and acid-soluble fraction (Co - 4.5, Ni - 23.5mgkg(-1)) were observed. The fractions of Co and Ni leachable from the ash in environmental conditions contain: 24.0% (Co) and 23.3% (Ni) of metal total amount in the industrial fly ash. The obtained mobility parameter of Co and Ni can be applied to estimate the concentration increase of mobile and hardly mobile forms of these metals in soil polluted with the ash.     

Estimating naphthenic acids concentrations in laboratory-exposed fish and in fish from the wild

Naphthenic acids (NAs) are the most water-soluble organic components found in the Athabasca oil sands in Alberta, Canada, and these acids are released into aqueous tailing waters as a result of bitumen extraction. Although the toxicity of NAs to fish is well known, there has been no method available to estimate NAs concentrations in fish. This paper describes a newly developed analytical method using single ion monitoring gas chromatography-mass spectrometry (GC-MS) to measure NAs in fish, down to concentrations of approximately 0.1mgkg(-1) of fish flesh. This method was used to measure the uptake and depuration of commercial NAs in laboratory experiments. Exposure of rainbow trout (Oncorhynchus mykiss) to 3mg NAsl(-1) for 9d gave a bioconcentration factor of approximately 2 at pH 8.2. Within 1d after the fish were transferred to NAs-free water, about 95% of the NAs were depurated. In addition, the analytical method was used to determine if NAs were present in four species of wild fish - northern pike (Esox lucius), lake whitefish (Coregonus clupeaformis), white sucker (Catostomus commersoni), walleye (Sander vitreus) - collected from near the oil sands. Flesh samples from 23 wild fish were analyzed, and 18 of these had no detectable NAs. Four fish (one of each species) contained NAs at concentrations from 0.2 to 2.8mgkg(-1). The GC-MS results from one wild fish presented a unique problem. However, with additional work it was concluded that the NAs concentration in this fish was <0.1mgkg(-1).     

A method for determining pyrene in mucus using synchronous fluorimetry with multiple standard additions

A new method was proposed to determine pyrene in mucus, which combined the synchronous fluorimetry with the multiple standard addition method (SFMSA). The method was used to determine pyrene in mucus directly without pretreatment. The method detection limit (MDL) for pyrene in mucus was measured as 0.47 ng/ml with a relative standard deviation of 12.7% (n = 7). The standard addition graph was linear in the range 0.05-50.00 ng/ml (r(2) = 0.9989). SFMSA was validated using a GC/MS method as a reference method, and nice agreement was found. The pyrene in mucus can be directly monitored by SFMSA without solvent extraction of samples. This indicates that SFMSA is more timesaving, less laborious and cheaper than the GC/MS method with solvent extraction. SFMSA has lower MDL and higher average recovery than the GC/MS method.     

Persistent chlorinated pesticides and polychlorinated biphenyls in selected fish species from Lake Tanganyika, Burundi, Africa

Concentrations of selected organochlorine pesticides and PCBs in seven fish species (cichlids) from the north end of the Lake Tanganyika, Burundi, Africa were determined. Results were compared to previous work on the Lake Tanganyika and other water bodies and to the European Community maximum residue levels (MRLs) in edible fat. The analytical method included a hot Soxhlet extraction with a mixture of acetone: hexane (1:3, v/v), gravimetrically lipid determination, and a single step clean-up. For PCBs and stable pesticides, the clean-up was done on activated silica gel impregnated with concentrated sulfuric acid, while for non acid-stable pesticides superposed layers of alumina, silica and florisil impregnated with 15% methanolic solution of KOH were successively used. Recoveries of organochlorine pesticides from certified reference material (CRM 430) were ranging from 86% for p,p'-DDT to 107% for endrin, while recoveries from blank fat spiked fortified at three different levels were between 65% for alachlor at the lowest fortification level and 107% for mirex at the highest fortification level. The limits of detection for each analyte were ranging from 0.1 ng/g to 0.5 ng/g fat. All chlorinated pesticides were found in the analyzed species but at low concentrations. Boulengerochromis microlepis contained the highest concentrations of HCHs (288.2 +/- 15.5 ng/g fat) and DDTs (909.1 +/- 42.5 ng/g fat), while the highest PCB levels (166.7 +/- 37.4 ng/g fat for the sum of 12 congeners) were found in Oreochromis niloticus. However, there is no evidence that Lake Tanganyika is more contaminated with pesticides than other African water bodies.     

Assays of PCB congeners and organochlorine insecticides with the transgenic Arabidopsis and tobacco plants carrying recombinant guinea pig AhR and GUS reporter genes

Certain congeners of polychlorinated biphenyls (PCBs) and organochlorine insecticides are ligands of aryl hydrocarbon receptors (AhRs) in animals. A recombinant guinea pig (g) AhR, XgDV, was constructed by fusing the ligand-binding domain of gAhR, the DNA-binding domain of LexA, and the transactivating domain of VP16. Then, the expression unit of β-glucuronidase (GUS) reporter gene regulated by XgDV was introduced into Arabidopsis and tobacco plants. When the transgenic Arabidopsis XgDV plants were cultured on Murashige-Skoog (MS) medium containing PCB congeners, the GUS activity in the plants increased toxic equivalent (TEQ)-dependently. The GUS activity in the transgenic Arabidopsis XgDV plants cultured on MS medium containing the organochlorine insecticide dieldrin was also induced. On the other hand, in the case of DDT, the GUS activity induced by 3-methylcholanthere in the plants decreased. The transgenic Arabidopsis XgDV plants detected 1000 ng g(-1) PCB126 in 1 g of soils. Thus the XgDV plants seemed to be useful for convenient assays of PCB congeners and organochlorine insecticides, without any extraction and purification steps.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.     

Optimisation of pressurised liquid extraction for elimination of sulphur interferences during determination of organotin compounds in sulphur-rich sediments by gas chromatography with flame photometric detection

A simple method for species-selective analysis of organotin compounds (OTCs) (butyl and phenyl) in sediments was developed. The sample preparation procedure was specifically optimised for sulphur-rich sediments to eliminate interferences from elemental sulphur and organosulphur compounds. Tin species were extracted from sediment samples using pressurised liquid extraction technique (PLE), ethylated - with simultaneous extraction to isooctane - in aqueous phase with sodium tetraethylborate (NaBEt(4)) and separated/detected by gas chromatography with flame photometric detection (GC-FPD). PLE operational variables (extraction temperature and pressure, solvent composition and number of static extraction steps) and extract handling routine were fine-tuned to minimise the amount of extracted interferents while keeping OTCs recovery at an acceptable level. Best results were obtained after extraction of sediment samples with methanol/water (75% v/v methanol) solution of acetic acid/sodium acetate with tropolone addition (0.6 g l(-1)). Derivatisation of low temperature, high-pressure (50 degrees C, 13.8 MPa) extracts gives isooctane extracts which are clean enough to be directly analysed by GC-FPD without any further cleanup. Interferences from elemental sulphur were completely eliminated while concentrations of other interferents were reduced to the level not impairing quantitation of OTCs under the study. No negative effects in terms of chromatographic column deterioration were observed after repeated injections of such extracts. Two certified reference materials, BCR646 and PACS-2, were analysed to assess performance of the method. Recoveries of all OTCs under the study, except MBT, were in the range of 91-114%. MBT extraction efficiency was low (34-47%) therefore the method is unsuitable for precise determinations of this compound.     

Toxicity of eight polycyclic aromatic compounds to red clover (Trifolium pratense), ryegrass (Lolium perenne), and mustard (Sinapsis alba)

The effect of eight polycyclic aromatic compounds (PACs) on the seed emergence and early life-stage growth of three terrestrial plants (Sinapsis alba, Trifolium pratense and Lolium perenne) were studied in a greenhouse, using a Danish agricultural soil with an organic carbon content of 1.6%. After three weeks of exposure, seed emergence and seedling weight (fresh weight and dry weight) were determined. Exposure concentrations were verified with chemical analysis. The substances tested were four polycyclic aromatic hydrocarbons (fluoranthene, pyrene, phenanthrene and fluorene), the N-, S-, and O-substituted analogues of fluorene (carbazole, dibenzothiophene and dibenzofuran, respectively), and the quinoline representative acridine. Seedling growth was a far more sensitive endpoint than seed emergence for all substances. Concentrations estimated to give a 20% reduction of seedling fresh weight (EC20-values) ranged from 36 to 290 mgkg(-1) for carbazole, 43 to 93 mgkg(-1) for dibenzofuran, 37 to 110 mgkg(-1) for dibenzothiophene, 140 to 650 mgkg(-1) for fluoranthene, 55 to 380 mgkg(-1) for fluorene, 37 to 300 mgkg(-1) for phenanthrene, and 49 to 1300 mgkg(-1) for pyrene. For acridine, no toxicity was observed within the concentration range tested (1-1000 mgkg(-1)). As illustrated by the EC20-values, there was a rather large difference in sensitivity between the species, and T. pratense was the most sensitive of the species tested.     

Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction

In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO(3) and 30 g anhydrous Na(2)SO(4) with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO(4) and primary secondary amine (PSA) sorbent. (14)C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method.     

Comparison of supercritical fluid extraction and Soxhlet extraction for the determination of PCBs in seaweed samples

The efficiency of supercritical fluid extraction for the determination of 12 polychlorinated biphenyls from algae samples is compared to Soxhlet extraction. Analytical detection limits for the individual congeners ranged from 0.62 microgl(-1) to 19 microgl(-1). Recovery was tested for both methods using standard addition procedure. At maximum spike level of concentration, the mean recoveries were not significantly different (P>0.05) of all PCBs studied, with the exception of PCBs 28, 52, 77 and 169. Method precision for Soxhlet extraction (< or =3.9%) was slightly better than for SFE (< or =9.2%). Although both methods yield comparable results, SFE offers the advantage of detecting all PCBs studied at lower concentrations, reducing extraction time, and reducing the amount of solvents needed. The optimized methods were applied to the analysis of three real seaweed samples, except for PCB101 the concentrations of all PCBs were low or below the detection limits. The levels of PCB101 found in sample 1 were 6.6+/-0.54 ng g(-1) d.w., in sample 2 the levels were 8.2+/-0.86 ng g(-1) d.w. and in sample 3 they were 7.7+/-0.08 ng g(-1) d.w.     

Selected ion chromatograms and tandem mass spectrometry for detection of trace polycyclic aromatic hydrocarbons in diesel exhaust

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10-30 pg for the smaller PAHs and 1-6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Toxicity of the explosive metabolites hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) and hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) to the earthworm Eisenia fetida

Toxicity of hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) to earthworm was evaluated. Both MNX and TNX had lethal and sublethal effects on earthworms. Exposure to MNX- or TNX-contaminated soil caused a significant concentration-dependent decrease in earthworm survival and growth. The lowest observed lethal concentration (LOLC) for both MNX and TNX was 100 and 200 mgkg(-1) soil dry weight in the sandy loam soil and in the silt loam soil, respectively. No earthworms survived for 14 days in MNX- or TNX-spiked soil at 500 mgkg(-1) soil dry weight. After 7 days exposure, the lowest observed effect concentration (LOEC) for earthworm growth was 50 mgkg(-1) soil dry weight for TNX and 100 mgkg(-1) soil dry weight for MNX in both soil types. The LC20 and LC50 for MNX in sandy loam soil were 114 and 262 mgkg(-1) and for TNX, they were 114 and 254 mgkg(-1) soil dry weight, respectively. The corresponding values for MNX and TNX in silt loam soil were 234 and 390 mgkg(-1) soil dry weight, respectively, and 200 and 362 mgkg(-1) soil dry weight, respectively. After 35 days exposure, earthworm growth was reduced 8-39% by TNX in sandy loam soil, whereas TNX only inhibited earthworm growth 5-18% at the same concentration range in silt loam soil. LC20 and LC50 for TNX were slightly lower than for MNX; this indicates that TNX was more toxic than MNX. No significant morphological or developmental abnormalities were observed in earthworms surviving exposure.     

Determination of antibiotic substances in hospital sewage water using solid phase extraction and liquid chromatography/mass spectrometry and group analogue internal standards

A method for determination of antibiotics in hospital sewage water has been developed and validated. Analogue internal standards for fluoroquinolones, sulfonamides, trimethoprim, beta-lactams (penicillins and cephalosporins), nitroimidazoles and tetracyclines were successfully used for calibration and shown to generally improve precision compared to external calibration. Matrix components caused ion suppression/enhancement effects during the MS detection for all analytes studied. Two effects were observed: general suppression and short-term variations in the MS response. In the hospital sewage water large temporal variations in the analyte concentration were observed during the course of the sampling period (seven grab samples in 13 h). Analyte concentrations varied within the following ranges (in microg l(-1)): ciprofloxacin, 3.6-101.0; metronidazole, 0.1-90.2; sulfamethoxazole, 0.4-12.8; ofloxacin, 0.2-7.6; trimethoprim, 0.6-7.6; and doxycycline, 0.6-6.7.     

A cost-effective screening method for pesticide residue analysis in fruits, vegetables, and cereal grains

This paper reports the results of studies performed to investigate the potential of applying thin layer chromatography (TLC) detection in combination with selected extraction and cleanup methods, for providing an alternative cost-effective analytical procedure for screening and confirmation of pesticide residues in plant commodities. The extraction was carried out with ethyl acetate and an on-line extraction method applying an acetone-dichloromethane mixture. The extracts were cleaned up with SX-3 gel, an adsorbent mixture of active carbon, magnesia, and diatomaceous earth, and on silica micro cartridges. The Rf values of 118 pesticides were tested in eleven elution systems with UV, and eight biotest methods and chemical detection reagents. Cabbage, green peas, orange, and tomatoes were selected as representative sample matrices for fruits and vegetables, while maize, rice, and wheat represented cereal grains. As an internal quality control measure, marker compounds were applied on each plate to verify the proper elution and detection conditions. The Rf values varied in the different elution systems. The best separation (widest Rf range) was achieved with silica gel (SG)--ethyl acetate (0.05-0.7), SG--benzene, (0.02-0.7) and reverse phase RP-18 F-254S layer with acetone: methanol: water/30:30:30 (v/v) (0.1-0.8). The relative standard deviation of Rf values (CV(Rf)) within laboratory reproducibility was generally less than 20%, except below 0.2 Rf, where the CVRf rapidly increased with decreasing Rf values. The fungi spore inhibition, chloroplast inhibition, and enzyme inhibition were found most suitable for detection of pesticides primarily for confirming their identity or screening for known substances. Their use for determination of pesticide residues in samples of unknown origin is not recommended.     

Monitoring of polychlorinated biphenyls in Belgian human adipose tissue samples

Polychlorinated biphenyls (PCBs) were monitored in Belgian human adipose tissue samples from deceased individuals (n=100). Their mean age was 52, ranging from 2 to 91 years. There were 57 men and 43 women. Other known variables were date of autopsy and place of residence. No information about diet or occupation was available. The seven marker congeners PCB 28, 52, 101, 118, 138, 153 and 180 were analysed in the samples with a GC-MS/MS method validated according to Commission Decision 2002/657/EC. Extracted fat was cleaned-up over a glass column filled with n-hexane, acid silica, deactivated alumina and anhydrous sodium sulfate. The whole procedure was subjected to a rigorous quality control programme with retention times, ion chromatograms and intensity ratios of the monitored product ions as identification criteria. The total PCB concentration ranged between 10 and 1640 ng g-1 fat, with a mean value of 658 ng g-1 fat. In the age groups of 0-9 (n=1), 10-19 (n=4), 20-29 (n=11), 30-39 (n=13), 40-49 (n=15), 50-59 (n=14), 60-69 (n=14), 70-79 (n=20), 80-89 (n=6) and 90-99 (n=2), the mean total PCB concentrations were 10, 134, 253, 445, 557, 687, 807, 962, 959, and 1191 ng g-1 fat, respectively. So, there was an increase of PCB body burden with age. For the male subjects (n=57; mean age of 53) the mean total PCB concentration was 633 ng g-1 fat. For the female subjects (n=43; mean age of 52) it was 690 ng g-1 fat. There was no significant sex-related difference in the concentrations of marker PCBs.     

Isomer specific synthesis using the Suzuki-coupling. Polychlorinated terphenyls as standards for environmental analysis

Defined polychlorinated terphenyl (PCT) single congeners as reference standards are the prerequisite for the development of analytical methods for their determination and quantification in the environment. The selective synthesis of PCTs for environmental analytical purposes by application of the Suzuki-coupling reaction is described. Under easily modified standard reaction conditions of this coupling process the PCTs can be obtained by reaction of benzeneboronic acids with dibromobenzenes mostly in good yields, as described by the synthesis of following PCT congeners: p-PCT (3,3("),5,5(")-tetrachloro-, 2,2("),4,4(")-tetrachloro-, 2('),3,3("),5,5(")-pentachloro-); m-PCT (3,3("),5,5(")-tetrachloro-) and o-PCT (3,3("),5,5(")-tetrachloro-). The terphenyl congeners were characterized by NMR (1H, 13C)- and FT-IR-spectroscopy. Their purity was checked by GC/MS analysis. The experimental and quantum-chemically calculated FT-IR-spectra were compared and it was shown, that the determination of the chlorine substitution pattern in the terphenyl congeners by their typical absorption spectra is possible.     

Validation of a pressurized solvent extraction and GC-NCI-MS method for the low level determination of 40 polybrominated diphenyl ethers in mothers' milk

This study reports an efficient method for the determination of 40 PBDEs from mono- to hepta-brominated in human milk. Pressurized liquid extraction (PLE) was optimized to recover PBDEs in a quantitative way using 1g of freeze dried milk. Due to the great amount of coextracted compounds, the clean-up step was optimized using alumina SPE disposable cartridges of 2 and 5g. Whereas 2g alumina SPE failed in providing good extraction yields, all PBDEs were satisfactorily recovered using 5g alumina SPE cartridges. Detection was performed with gas chromatography coupled to mass spectrometry with negative chemical ionization and method detection limits ranged from 0.01 to 0.05mugkg(-1) wet weight (ww) with a good intra and inter-day variation (coefficient of variation lower than 13.4%). This method was validated by participating in an interlaboratory exercise from Quasimeme (United Kingdom), where a standard solution containing seven congeners and a certified unspiked mothers' milk were analyzed. In the standard mixture, levels between 96.915 and 570.172mugl(-1) were quantified, whereas in certified mothers' milk, BDEs 47, 99, 100 and 154 were detected at levels from 0.010 and 0.061mugkg(-1) ww, with an error <30%. The applicability of the method was tested experimentally in five mothers' milk samples, where only BDE 47 was detected at a maximum concentration of 10.45mugkg(-1) lipid weight (lw). PLE succeeded in extracting all PBDEs from the sample with good reproducibility although the clean-up step had to be severely performed to eliminate sample interferences such as milk lipids and proteins.     

Polychlorinated naphthalenes (PCNs) in Irish foods: Occurrence and human dietary exposure

The concentrations of selected polychlorinated naphthalene (PCN) congeners (PCNs 52, 53, 66/67, 68, 69, 71/72, 73, 74 and 75) were determined in 100 commonly consumed foods, in the first study on occurrence of these contaminants in the Republic of Ireland. Congener selection was based on current knowledge on PCN occurrence and toxicology, and the availability of reliable reference standards. The determinations were carried out using validated analytical methodology based on 13C10 labelled internal standardisation and measurement by HRGC-HRMS. The results showed PCN occurrence in the majority of studied foods--milk, fish, dairy and meat products, eggs, animal fat, shellfish, offal, vegetables, cereal products, etc. ranging from 0.09 ng kg(-1) whole weight for milk to 59.3 ng kg(-1) whole weight for fish, for the sum of the measured PCNs. The most frequently detected congeners were PCNs 66/67, PCN 52, and PCN 73. The highest concentrations were observed in fish, which generally showed congener profiles that reflect some commercial mixtures. The data compares well with other recently reported data for Western Europe. The dioxin-like toxicity (PCN TEQ) associated with these concentrations is lower than that reported for chlorinated dioxins or PCBs in food from Ireland. The dietary exposure of the Irish adult population to PCNs was calculated following a probabilistic approach, using the full dataset of occurrence and current consumption data. The estimates of dietary intakes at approximately 0.14 pg TEQ kg bw(-1) month(-1) for adults on an average diet, reflects the relatively lower occurrence levels.     

Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).