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1.
Ecotoxicol Environ Saf ; 165: 343-348, 2018 Dec 15.
Article in English | MEDLINE | ID: mdl-30212735

ABSTRACT

Polybrominated diphenyl ethers (PBDEs) in the feather and muscle of common kestrels (Falco tinnunculus), eagle owls (Bubo bubo) and little owls (Athene noctua) collected from Beijing, China were investigated. The concentrations of ∑23PBDEs in the muscle and feather of all the birds of prey ranged from 46 to 7.77 × 104 ng/g lipid weight (lw; median 241 ng/g lw) and 1.50-191 ng/g dry weight (dw; median 21.1 ng/g dw), respectively. Higher brominated congeners, e.g., BDE-209, -153, -207 and -196 were the dominant congeners in both feather and muscle. However, the concentrations of lower brominated congeners in feather were significantly correlated with those in muscle (p < 0.05), which suggested that feather could efficiently reflect lower brominated BDEs in the internal tissue of birds of prey. The calculated hazard quotients (HQs) > 10 in common kestrel and little owl suggested that the high levels of PBDEs posed potentially high risk to some birds of prey living in Beijing area.


Subject(s)
Falconiformes , Feathers/chemistry , Halogenated Diphenyl Ethers/analysis , Muscle, Skeletal/chemistry , Strigiformes , Animals , Beijing , Bromine Compounds/analysis , Environmental Monitoring
2.
Anal Bioanal Chem ; 409(22): 5307-5317, 2017 Sep.
Article in English | MEDLINE | ID: mdl-28741109

ABSTRACT

Commonly, analytical methods measuring brominated flame retardants (BFRs) of different chemical polarities in human serum are labor consuming and tedious. Our study used acidified diatomaceous earth as solid-phase extraction (SPE) adsorbent and defatting material to simultaneously determine the most abundant BFRs and their metabolites with different polarities in human serum samples. The analytes include three types of commercial BFRs, tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) isomers, and polybrominated biphenyl ethers (PBDEs), and dominant hydroxylated BDE (OH-PBDE) and methoxylated BDE (MeO-PBDE) metabolites of PBDEs. The sample eluents were sequentially analyzed for PBDEs and MeO-BDEs on online gel permeation chromatography/gas chromatography-electron capture-negative ionization mass spectrometry (online GPC GC-ECNI-MS) and for TBBPA, HBCD, and OH-BDEs on liquid chromatography-tandem mass spectrometry (LC-MS/MS). Method recoveries were 67-134% with a relative standard deviation (RSD) of less than 20%. Method detection limits (MDLs) were 0.30-4.20 pg/mL fresh weight (f.w.) for all analytes, except for BDE-209 of 16 pg/mL f.w. The methodology was also applied in a pilot study, which analyzed ten real samples from healthy donors in China, and the majority of target analytes were detected with a detection rate of more than 80%. To our knowledge, it is the first time for us in effectively determining BFRs of most types in one aliquot of human serum samples. This new analytical method is more specific, sensitive, accurate, and time saving for routine biomonitoring of these BFRs and for integrated assessment of health risk of BFR exposure.


Subject(s)
Blood Chemical Analysis/methods , Flame Retardants/analysis , Halogenated Diphenyl Ethers/blood , Bromine Compounds/analysis , Halogenated Diphenyl Ethers/metabolism , Humans , Limit of Detection , Quality Control , Solid Phase Extraction , Time Factors
3.
Acta Pol Pharm ; 74(2): 401-404, 2017 Mar.
Article in English | MEDLINE | ID: mdl-29624245

ABSTRACT

Three new methods were developed for the quantitative determination of mesalazine in the form of the pure substance or in the form of suppositories and tablets - accordingly: bromatometric, diazotization and visible light spectrophotometry method. Optimizing the time and the temperature of the bromination reaction (50°C, 50 min) 4-amino-2,3,5,6-tetrabromophenol was obtained. The results obtained were reproducible, accurate and precise. Developed methods were compared to the pharmacopoeial approach - alkalimetry in an aqueous medium. The validation parameters of all methods were comparable. Developed methods for quantification of mesalazine are a viable alternative to other more expensive approaches.


Subject(s)
Anti-Inflammatory Agents, Non-Steroidal/analysis , Bromine Compounds/analysis , Diazonium Compounds/analysis , Mesalamine/analysis , Spectrophotometry/methods , Anti-Inflammatory Agents, Non-Steroidal/chemistry , Bromine Compounds/chemistry , Chemistry, Pharmaceutical , Diazonium Compounds/chemistry , Drug Compounding , Kinetics , Mesalamine/chemistry , Reproducibility of Results , Suppositories , Tablets , Temperature
4.
Environ Sci Technol ; 50(1): 321-30, 2016 Jan 05.
Article in English | MEDLINE | ID: mdl-26618527

ABSTRACT

Previously unreported natural and synthetic organo-bromine compounds (NSOBCs) have been found to contribute more than 99% of total organic bromine (TOB) in environmental matrices. We recently developed a novel untargeted method (data-independent precursor isolation and characteristic fragment, DIPIC-Frag) and identified ∼2000 NSOBCs in two sediments from Lake Michigan. In this study, this method was used to investigate the distributions of these NSOBCs in 23 surficial samples and 24 segments of a sediment core from Lake Michigan. NSOBCs were detected in all 23 surficial samples and exhibited 10- to 100-fold variations in peak abundance among locations. The pattern of distributions of NSOBCs was correlated with depth of the water column (r(2) = 0.61, p < 0.001). Hierarchical cluster analysis showed that sediments in close proximity exhibited similar profiles of NSOBCs. Distributions of NSOBCs in 24 segments of a sediment core dated from 1766 to 2008 were investigated, and samples from similar depths exhibited similar profiles of NSOBCs. NSOBCs were grouped into four clusters (soft-cluster analysis) with different temporal trends of abundances. 515 and 768 of the NSOBCs were grouped into cluster 1 and cluster 3 with increasing temporal trends, especially since 1950, indicating that abundances of these compounds might have been affected by human activities.


Subject(s)
Bromine Compounds/analysis , Geologic Sediments/chemistry , Halogenated Diphenyl Ethers/analysis , Hydrocarbons, Brominated/analysis , Lakes/chemistry , Water Pollutants, Chemical/analysis , Environmental Monitoring/methods , Michigan
5.
J Hazard Mater ; 283: 551-7, 2015.
Article in English | MEDLINE | ID: mdl-25464295

ABSTRACT

Electrochemical advanced oxidation processes (EAOPs) have been widely investigated as promising technologies to remove trace organic contaminants from water, but have rarely been used for the treatment of real waste streams. Anodic oxidation with a boron-doped diamond (BDD) anode was applied for the treatment of secondary effluent from a municipal sewage treatment plant containing 29 target pharmaceuticals and pesticides. The effectiveness of the treatment was assessed from the contaminants decay, dissolved organic carbon and chemical oxygen demand removal. The effect of applied current and pH was evaluated. Almost complete mineralization of effluent organic matter and trace contaminants can be obtained by this EAOP primarily due to the action of hydroxyl radicals formed at the BDD surface. The oxidation of Cl(-) ions present in the wastewater at the BDD anode gave rise to active chlorine species (Cl2/HClO/ClO(-)), which are competitive oxidizing agents yielding chloramines and organohalogen byproducts, quantified as adsorbable organic halogen. However, further anodic oxidation of HClO/ClO(-) species led to the production of ClO3(-) and ClO4(-) ions. The formation of these species hampers the application as a single-stage tertiary treatment, but posterior cathodic reduction of chlorate and perchlorate species may reduce the risks associated to their presence in the environment.


Subject(s)
Boron , Diamond , Electrochemistry/methods , Pesticides/chemistry , Pharmaceutical Preparations/chemistry , Water Purification/methods , Biological Oxygen Demand Analysis , Bromine Compounds/analysis , Electrodes , Hydrocarbons, Chlorinated/analysis , Hydroxyl Radical/analysis , Oxidation-Reduction , Sewage/chemistry , Wastewater/chemistry , Water Pollutants, Chemical/chemistry
6.
Article in English | MEDLINE | ID: mdl-24040839

ABSTRACT

In order to screen for the presence of a recycled polymer waste stream from waste electric and electronic equipment (WEEE), a market survey was conducted on black plastic food-contact articles (FCA). An analytical method was applied combining X-ray fluorescence spectrometry (XRF) with thermal desorption gas chromatography coupled with mass spectrometry (thermal desorption GC-MS). Firstly, XRF spectrometry was applied to distinguish bromine-positive samples. Secondly, bromine-positive samples were submitted for identification by thermal desorption GC-MS. Generally, the bromine-positive samples contained mainly technical decabromodiphenyl ether (decaBDE). Newer types of BFRs such as tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bis(2,3-dibromopropyl), ether (TBBPA-BDBPE) and decabromodiphenylethane (DBDPE), replacing the polybrominated diphenyleters (PBDEs) and polybrominated diphenyls (PBBs), were also identified. In none of the tested samples were PBBs or hexabromocyclododecane (HBCD) found. Polymer identification was carried out using Fourier-transformed infrared spectroscopy measurement (FTIR) on all samples. The results indicate that polypropylene-polyethylene copolymers (PP-PE) and mainly styrene-based food-contact materials, such as acrylonitrile-butadiene-styrene (ABS) have the highest risk of containing BFRs.


Subject(s)
Bromine Compounds/analysis , Cooking and Eating Utensils , Flame Retardants/analysis , Food Packaging/instrumentation , Acrylic Resins/chemistry , Bromine/analysis , Butadienes/chemistry , Europe , Food Contamination/analysis , Gas Chromatography-Mass Spectrometry , Polybrominated Biphenyls/analysis , Polyethylenes/chemistry , Polymers/analysis , Polypropylenes/chemistry , Polystyrenes/chemistry , Spectrometry, X-Ray Emission , Spectroscopy, Fourier Transform Infrared
7.
Environ Int ; 60: 202-8, 2013 Oct.
Article in English | MEDLINE | ID: mdl-24071021

ABSTRACT

The analysis of temporal trends is a key tool to assess the success of national and international regulations on chemical pollution. Persistent organic pollutants (POPs) are chemical pollutants, which are not only harmful, but also because of their slow environmental degradation they pose a long-time risk. In this study, concentrations of selected POPs were measured between 1993 and 2012 in digested sewage sludge from eight municipal waste water treatment plants. Polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-dioxins and furans (PCDD/Fs), which have been banned or restricted for decades, exhibited decreasing trends with apparent half-lives between 9 and 12years. Polybrominated diphenyl ethers (PBDEs) and long-chain perfluorinated acids showed no clear trend, which reflects the recent introduction of regulations. The analysis of octabromodiphenyl ethers did not reveal indications for reductive debromination of decabromodiphenyl ether; however the analysis of total bromine showed that up to 14% of the total bromine load in sewage sludge originated from PBDEs (average 2%). This is the first study to report temporal trends for more than 20years of series POPs in sewage sludge.


Subject(s)
Bromine Compounds/analysis , Environmental Monitoring/statistics & numerical data , Environmental Pollutants/analysis , Halogenated Diphenyl Ethers/analysis , Polychlorinated Biphenyls/analysis , Polychlorinated Dibenzodioxins/analysis , Sewage/analysis , Benzofurans/analysis , Conservation of Natural Resources , Dioxins/analysis , Switzerland , Time Factors
8.
Ecotoxicol Environ Saf ; 88: 55-64, 2013 Feb.
Article in English | MEDLINE | ID: mdl-23219662

ABSTRACT

Information on the occurrence of persistent organic pollutants (POPs) in fish from Tunisia is scarce. In this study, thirty one persistent organic pollutants including organochlorine pesticides (OCPs) (dichlorodihenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB)), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were determined in solea solea muscle, from Bizerte Lagoon (northern Tunisia) and from the Mediterranean Sea (reference area) (northern Mediterranean). In the Bizerte Lagoon, contaminant concentrations generally followed this order: PCBs>DDTs>PBDEs>MeO-PBDEs>HCB>HCHs; while in the Mediterranean Sea, pollutant concentration followed this order: MeO-PBDEs>PCBs>DDTs>PBDEs>HCB>HCHs. Mean levels of organochlorine compounds were 1018 and 380 ng g(-1) lipid weight (lw) in fish from Bizerte Lagoon and the Mediterranean Sea, respectively. Mean concentrations of organobromine compounds were 279 and 301 ng g(-1) lw in sole from Bizerte Lagoon and the Mediterranean Sea, respectively. Organohalogen concentrations in fish from Bizerte Lagoon were similar or slightly lower than those reported for other marine fish species from other locations around the world. PCB, HCH, HCB and PBDE levels were negatively correlated with lipid content, while no such correlation was seen for DDTs. Assessment based on several available guidelines suggested an insignificant human health risk for dietary intake of HCB, lindane and PBDEs associated with consumption of sole. However, the estimated lifetime cancer risk from dietary exposure to DDTs and PCBs is a potential concern.


Subject(s)
Bromine Compounds/analysis , Environmental Monitoring , Flatfishes/physiology , Food Safety , Hydrocarbons, Chlorinated/analysis , Muscles/chemistry , Water Pollutants, Chemical/analysis , Animals , Bromine Compounds/metabolism , Flatfishes/metabolism , Food Chain , Humans , Hydrocarbons, Chlorinated/metabolism , Mediterranean Sea , Risk Assessment , Tunisia , Water Pollutants, Chemical/metabolism
9.
J Environ Monit ; 14(12): 3156-63, 2012 Dec.
Article in English | MEDLINE | ID: mdl-23124546

ABSTRACT

Atmospheric concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) were measured in Taizhou, a large electronic equipment waste (e-waste) recycling area in East China. The mean concentrations (in summer and winter) of PCDD/Fs (0.45 and 0.39 pg WHO-TEQ m⁻³, where WHO-TEQ is the toxic equivalent set by the World Health Organisation), PBDD/Fs (0.22 and 0.18 pg WHO-TEQ m⁻³), and PBDEs (270 and 225 pg m⁻³) in this region have declined compared with those in 2005, due to regulations on primitive e-waste recycling activities. However, these concentrations remain higher than the historically highest levels in Europe and North America. The congener profiles of 2,3,7,8-substituted PCDD/Fs were similar, with OCDD, 1,2,3,4,6,7,8-HpCDF, OCDF, and 1,2,3,4,6,7,8-HpCDD being the most abundant congeners at all sites. The PCDD/F homologue profiles in the present study were different from those typically observed at non-e-waste locations, indicating a distinct source in this region. Seasonal differences were found in the lower brominated PBDE profiles. These differences indicate that the PBDE emission sources in summer (e.g., strong evaporation sources) differed from those in winter. However, the relatively steady congener profiles of the highly brominated PBDEs suggest that these PBDEs were controlled primarily by similar emission mechanisms. The lifetime excess cancer risks from exposure to PCDD/Fs and PBDD/Fs via inhalation ranged from 0.7 × 10⁻5 to 5.4 × 10⁻5, or approximately 80 cancer cases in the Taizhou population.


Subject(s)
Air Pollutants/analysis , Benzofurans/analysis , Dioxins/analysis , Electronic Waste/analysis , Halogenated Diphenyl Ethers/analysis , Neoplasms/epidemiology , Polychlorinated Dibenzodioxins/analogs & derivatives , Air Pollutants/toxicity , Air Pollution/statistics & numerical data , Benzofurans/toxicity , Bromine Compounds/analysis , Bromine Compounds/toxicity , China/epidemiology , Dioxins/toxicity , Electronic Waste/statistics & numerical data , Environmental Exposure/statistics & numerical data , Environmental Monitoring , Halogenated Diphenyl Ethers/toxicity , Humans , Polychlorinated Dibenzodioxins/analysis , Polychlorinated Dibenzodioxins/toxicity , Polymers/analysis , Polymers/toxicity , Risk Assessment
10.
Environ Sci Technol ; 46(19): 10704-10, 2012 Oct 02.
Article in English | MEDLINE | ID: mdl-22889080

ABSTRACT

We report an instrument designed for trace gas measurement of highly reactive halogenated radicals, such as bromine oxide and iodine oxide, as well as for nitrogen dioxide and formaldehyde. This compact and robust spectrometer relies on an alternated injection of a frequency-doubled femtosecond radiation at 338 and 436 nm into two parallel high-finesse cavities, for measuring BrO + H(2)CO, and IO + NO(2), respectively. The transmission of the broadband radiation through the cavity is analyzed with a high resolution, compact spectrograph consisting of an echelle grating and a high sensitivity CCD camera. The transportable instrument fits on a breadboard 120 × 60 cm size and is suitable for in situ and real time measurements of these species. A field campaign at the Marine Boundary Layer in Roscoff (in the northwest of France, 48.7°N, 4.0°W) during June 2011 illustrates the outstanding performance of the instrument, which reaches a bandwidth normalized minimum absorption coefficient of 1.3 × 10(-11) cm(-1) Hz(-1/2) per spectral element, and provides detection levels as low as 20 parts per quadrillion of IO in 5 min of acquisition.


Subject(s)
Air Pollutants/analysis , Bromine Compounds/analysis , Iodine Compounds/analysis , Nitrogen Dioxide/analysis , Oxides/analysis , Spectrum Analysis/instrumentation , Spectrum Analysis/methods , Equipment Design , Formaldehyde/analysis , France , Limit of Detection , Sensitivity and Specificity
11.
J Environ Monit ; 14(7): 1935-42, 2012 Jul.
Article in English | MEDLINE | ID: mdl-22641387

ABSTRACT

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.


Subject(s)
Benzofurans/analysis , Bromine Compounds/analysis , Chlorine Compounds/analysis , Dioxins/analysis , Geologic Sediments/chemistry , Water Pollutants, Chemical/analysis , China , Environmental Monitoring , Lakes/chemistry , Water Pollution, Chemical/statistics & numerical data
12.
Water Res ; 46(3): 828-36, 2012 Mar 01.
Article in English | MEDLINE | ID: mdl-22153961

ABSTRACT

Despite evidence of formation of brominated compounds in seawater swimming pools treated with chlorine, no data about exposure levels to these compounds have been reported. To address this issue, a survey has been carried out in four establishments (representing 8 pools) fed with seawater and devoted to relaxing and cure treatments (thalassotherapy centres located in Southeast of France). Carcinogenic and mutagenic brominated disinfection byproducts (trihalomethanes -THM- and halogenated acetic acids -HAA-) were quantified at varying levels, statistically related to organic loadings brought by bathers, and not from marine organic matter, and also linked to activities carried out in the pools (watergym vs swimming). Bromoform and dibromoacetic acid, the most abundant THM and HAA detected, were measured at levels up to 18-fold greater than the maximum contaminant levels of 60 and 80 µg/L fixed by US.EPA in drinking waters. The correlations between these disinfection byproducts and other environmental factors such as nitrogen, pH, temperature, free residual chlorine, UV(254), chloride and bromide concentrations, and daily frequentation were examined. Because thalassotherapy and seawater swimming pools (hotels, cruise ships,…) are increasing in use around the world and because carcinogenic and mutagenic brominated byproducts may be produced in chlorinated seawater swimming pools, specific care should be taken to assure cleanliness of users (swimmers and patients taking the waters) and to increase water circulation through media filters to reduce levels of brominated byproducts.


Subject(s)
Bromine Compounds/analysis , Chlorine/chemistry , Environmental Exposure/analysis , Seawater/chemistry , Swimming Pools , Acetic Acid/analysis , Analysis of Variance , Carbon/analysis , Statistics, Nonparametric , Trihalomethanes/analysis , Ultraviolet Rays
13.
Chemosphere ; 83(10): 1360-5, 2011 May.
Article in English | MEDLINE | ID: mdl-21458020

ABSTRACT

Concentrations of several "novel" brominated flame retardants (NBFRs) are reported in indoor dust samples from Belgian houses (n=39) and offices (n=6) and from day-care centers and schools in the West Midlands of the UK (n=36). Using a GC-ECNI/MS method, the following NBFRs were quantified: decabromodiphenyl ethane (DBDPE) (range <20-2470 ng g(-1)), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (range <0.5-1740 ng g(-1)), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE) (range <20-9960 ng g(-1)), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (range <2-436 ng g(-1)) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (range <2-6175 ng g(-1)). Hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), another NBFR, was below the detection limit of 2 ng g(-1) dust in all dust samples. No correlation was detected between concentrations of NBFRs and PBDEs. The ratio of TBB:TBPH in the dust samples ranged from 0.01 to 4.77 (average 0.42), compared to the ratio present in the commercial flame retardant product FM 550 (TBB:TBPH=4:1). Furthermore, no correlation was detected between concentrations in dust of TBB and TBPH. This may suggest different sources of these NBFRs, or similar sources but compound-specific differences in their indoor fate and transport. Exposure via dust ingestion was estimated for both adults and toddlers under low-end (5th percentile), typical (median), and high-end (95th percentile concentrations) scenarios. These were calculated assuming 100% absorption of intake dust and using mean dust ingestion (adults=20 mg d(-1); for toddlers=50 mg d(-1)) and high dust ingestion (adults=50 mg d(-1); for toddlers=200 mg d(-1)). Typical exposure with high dust ingestion estimates for adults were 0.01, 0.2, 0.01, 0.02 and 0.08 ng kg(-1) bw d(-1) and for toddlers 0.05, 1.9, 0.08, 0.4 and 1.12 ng kg(-1) bw d(-1) for BTBPE, DBDPE, TBB, TBPH and TBBPA-DBPE, respectively. Our results showed that, similar to PBDEs, toddlers have higher exposure to NBFRs than adults. This study documents the presence of NBFRs in indoor environments, and emphasizes the need to evaluate the health implications of exposure to such chemicals.


Subject(s)
Air Pollutants/analysis , Air Pollution, Indoor/analysis , Bromine Compounds/analysis , Dust/analysis , Flame Retardants/analysis , Adult , Air Pollution, Indoor/statistics & numerical data , Belgium , Child , Child Day Care Centers/statistics & numerical data , Child, Preschool , Environmental Monitoring , Housing/statistics & numerical data , Humans , Infant , Inhalation Exposure/statistics & numerical data , United Kingdom , Workplace/statistics & numerical data
14.
J Chromatogr A ; 1218(20): 3095-104, 2011 May 20.
Article in English | MEDLINE | ID: mdl-21489539

ABSTRACT

The mechanism underlying the enrichment power by pressure-assisted electrokinetic injection (PAEKI) in capillary electrophoresis (CE) was investigated for on-line pre-concentration of arsenic [As(III) and As(V)], selenium [Se(IV) and Se(VI)] and bromate (BrO(3)(-)). Analyte diffusion behaviour from PAEKI sample plugs were evaluated by monitoring peak broadening as a function of stagnant time and position in the capillary. During PAEKI, anionic analytes accumulate at the sample-separation buffer boundary. We proposed that a counter-ion layer formed in PAEKI, where a cation layer was formed at the separation buffer side of boundary. The cation layer served as a soft boundary which impeded zone broadening via electrostatic attraction between layers. This effect likely played an important role in maintaining focused analyte bands by suppressing diffusion. Comparison of analyte behaviour in PAEKI injected sample plugs to behaviour in hydrodynamically injected ones proved the existence of a counter-ion layer. The dependence of analyte diffusion in PAEKI plugs on electrochemical properties (viscosity, conductivity, electrophoretic mobility) further supported the hypothesis. Additionally, it was noted that analytes with low electrophoretic mobility were more efficiently pre-concentrated by PAEKI and were less subject to forces of dispersion than analytes with greater electrophoretic mobility. PAEKI-CE coupled to electrospray tandem mass spectroscopy (ESI-MS/MS) was then optimized and validated for detection of arsenic, selenium and bromate in water samples. On-line enrichment of the target analytes was achieved with 1-3 ng mL(-1) detection limits, which was below the maximum contaminant levels in drinking water for all five anions studied. Noteworthy, the potential of the method for unbiased detection of molecular species in untreated water was demonstrated. No contamination was detected in the water samples tested; however, recovery was 90-118% for spiked samples. The method was demonstrated be comparable to current methods for detection of inorganic contaminants in drinking water and is a good alternative method to ion chromatography/liquid chromatography-MS.


Subject(s)
Electrophoresis, Capillary/methods , Inorganic Chemicals/analysis , Spectrometry, Mass, Electrospray Ionization/methods , Water Pollutants, Chemical/analysis , Water Supply/analysis , Acetonitriles/chemistry , Arsenicals/analysis , Bromine Compounds/analysis , Diffusion , Linear Models , Pressure , Selenium Compounds/analysis , Tandem Mass Spectrometry/methods , Viscosity
15.
Chemosphere ; 83(7): 948-54, 2011 May.
Article in English | MEDLINE | ID: mdl-21402396

ABSTRACT

The 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1, MBP-79) and further halogenated 1'-methyl-1,2'-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was renewed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br(2) to give 30.5mg BrCl(6)-MBPs along with lower proportions of Br(2)Cl(5)-, Br(3)Cl(4)-, Br(4)Cl(3)- and traces of Br(5)Cl(2)-MBPs. Longer UV-irradiation in the presence of Br(2) even allowed for the detection of Br(6)Cl-MBPs and traces of Br(7)-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl(6)-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl(6)-MBP (∼1.5mg) was characterized by GC/MS and (13)C NMR to be 2-bromo-3,3',4,4',5,5'-hexachloro-1-methyl-1,2'-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a ß-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl(6)-MBP enantiomers could be trapped.


Subject(s)
Biological Products/chemistry , Bromine Compounds/chemical synthesis , Chlorine Compounds/chemical synthesis , Hydrocarbons, Chlorinated/chemistry , Pyrroles/chemistry , Water Pollutants, Chemical/chemical synthesis , Biological Products/analysis , Bromine Compounds/analysis , Chlorine Compounds/analysis , Hydrocarbons, Chlorinated/analysis , Isomerism , Magnetic Resonance Spectroscopy , Photochemical Processes , Pyrroles/analysis , Ultraviolet Rays , Water Pollutants, Chemical/analysis
16.
Chemosphere ; 83(6): 783-91, 2011 Apr.
Article in English | MEDLINE | ID: mdl-21429558

ABSTRACT

In this study, soil contamination by PCBs, PBDEs, HBCDs and two novel BFRs such as 1,2-bis-(2,4,6-tribromopenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in various locations such as industrial, urban, rural, dumping site and agricultural areas of Surabaya, Indonesia has been characterized in order to evaluate their contamination status, profiles, potential sources, fate and behavior. Range and median concentrations of PCBs, PBDEs, HBCDs, BTBPE and DBDPE were ND - 9.6 (1.2), 0.069 - 24 (7.4), ND - 1.8 (0.48), ND - 1.7 (0.14) and ND - 7.6 (2.2) ng g(-1)dw, respectively. Industrial, urban and dumping areas were inventoried as the main sources of these pollutants. Decreasing gradient levels were observed for these contaminants from industrial district, urban, dumping site, rural and agricultural areas, in that order. Furthermore, organic carbon contents and proximity to the point sources were found as the major controlling factors. Contaminant profiles were characterized by the predominance of hexa-, hepta- and penta-homologues for PCBs; deca-, nona- and octa- for PBDEs and α-isomer for HBCDs. Product mixtures such as Ar1260/KC600 and Ar1254/KC500 for PCBs, deca- and octa-BDEs for PBDEs were the possible common formulations used in study area. To our knowledge, this is a first comprehensive study on characterization of soil contamination by PCBs, PBDEs and HBCDs together with two novel BFRs in a highly industrialized city located in tropical region. This study provides baseline information for establishing national monitoring programs in Indonesia.


Subject(s)
Bromine Compounds/analysis , Flame Retardants/analysis , Polychlorinated Biphenyls/analysis , Soil Pollutants/analysis , Bromobenzenes/analysis , Environmental Monitoring , Indonesia , Soil/chemistry
17.
Environ Pollut ; 159(6): 1577-83, 2011 Jun.
Article in English | MEDLINE | ID: mdl-21421283

ABSTRACT

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó10PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to -492 and -1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.


Subject(s)
Air Pollutants/analysis , Flame Retardants/analysis , Halogenated Diphenyl Ethers/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Air Movements , Arctic Regions , Atmosphere/chemistry , Bromine Compounds/analysis , Bromobenzenes/analysis , Environmental Monitoring , Europe , Hydrocarbons, Brominated/analysis , Particulate Matter/analysis , Toluene/analogs & derivatives , Toluene/analysis
18.
Environ Sci Technol ; 45(5): 1917-25, 2011 Mar 01.
Article in English | MEDLINE | ID: mdl-21309600

ABSTRACT

This study investigated the homogeneous gas-phase formation of polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs) from 2-BP, 2,4-DBP, and 2,4,6-TBP as precursors. First, density functional theory (DFT) calculations were carried out for the formation mechanism. The geometries and frequencies of the stationary points were calculated at the MPWB1K/6-31+G(d,p) level, and the energetic parameters were further refined by the MPWB1K/6-311+G(3df,2p) method. Then, the formation mechanism of PBDD/Fs was compared and contrasted with the PCDD/F formation mechanism from 2-CP, 2,4-DCP, and 2,4,6-TCP as precursors. Finally, the rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600-1200 K. Present results indicate that only BPs with bromine at the ortho position are capable of forming PBDDs. The study, together with works already published from our group, clearly shows an increased propensity for the dioxin formations from BPs over the analogous CPs. Multibromine substitutions suppress the PBDD/F formations.


Subject(s)
Air Pollutants/chemistry , Benzofurans/chemistry , Bromine Compounds/chemistry , Dioxins/chemistry , Phenols/chemistry , Air Pollutants/analysis , Air Pollutants/chemical synthesis , Benzofurans/analysis , Benzofurans/chemical synthesis , Bromine Compounds/analysis , Bromine Compounds/chemical synthesis , Dioxins/analysis , Dioxins/chemical synthesis , Kinetics , Phenols/analysis
19.
Chemosphere ; 83(2): 95-103, 2011 Mar.
Article in English | MEDLINE | ID: mdl-21284993

ABSTRACT

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 µg kg(-1)) gave maximum fillet levels of 22 µg kg(-1), which exceeds the estimated permissible level (21 µg kg(-1)) for toxaphene in fish food samples in Norway.


Subject(s)
Flame Retardants/analysis , Pesticides/analysis , Polychlorinated Biphenyls/analysis , Polychlorinated Dibenzodioxins/analogs & derivatives , Salmo salar/metabolism , Water Pollutants, Chemical/analysis , Animal Feed/analysis , Animals , Benzofurans/analysis , Benzofurans/metabolism , Bromine Compounds/analysis , Bromine Compounds/metabolism , Dibenzofurans, Polychlorinated , Diet/statistics & numerical data , Environmental Exposure/analysis , Environmental Exposure/statistics & numerical data , Flame Retardants/metabolism , Humans , Hydrocarbons, Chlorinated/analysis , Hydrocarbons, Chlorinated/metabolism , Pesticides/metabolism , Polychlorinated Biphenyls/metabolism , Polychlorinated Dibenzodioxins/analysis , Polychlorinated Dibenzodioxins/metabolism , Seafood/analysis , Water Pollutants, Chemical/metabolism
20.
Environ Sci Technol ; 45(5): 1820-6, 2011 Mar 01.
Article in English | MEDLINE | ID: mdl-21291232

ABSTRACT

Seawater and air samples were collected aboard the FS Polarstern during the cruises ANT-XXV/1 + 2 in the Atlantic and Southern Ocean in 2008. The particulate and dissolved phase in water and particulate and gaseous phase in air were analyzed separately for nine polybrominated diphenyl ethers (PBDEs) and six non-PBDE brominated flame retardants (BFRs). Air concentrations of 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and hexabromobenzene (HBB) in the gaseous and particulate phase (median = 0.56 pg m(-3) for DPTE and 0.92 pg m(-3) for HBB) were comparable to ∑(9)PBDEs (1.0 pg m(-3)). Pentabromotoluene (PBT) was detectable in ∼30% of the gaseous phase samples, whereas concentration of 2,4,6-tribromophenyl allylether (ATE), hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) and 2-ethyl-1-hexyl 2,3,4,5-tetrabromobenzoate (EHTBB) were below their method detection limits. DPTE, and PBDEs were also found in seawater at low pg per liter levels. Elevated seawater concentrations of PBDEs and DPTE were measured in the English Channel and close to South African coast. Concentrations of DPTE, BDE-47, and BDE-99 in the atmosphere generally decreased from Europe toward the Southern Ocean, whereas no latitudinal trend was observed in seawater. Air-water exchange gradients suggested net deposition dominates for all selected substances. The medians of net deposition fluxes for the air-water gas exchange were 83, 21, 69, 20, and 781 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB, whereas medians of dry deposition fluxes were 2.0, 0.3, 1.2, 1.0, and 0.5 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB. Overall, these results highlight the important role of the long-range atmospheric transport of PBDE and non-PBDE BFRs to remote regions.


Subject(s)
Air Pollutants/analysis , Atmosphere/chemistry , Bromine Compounds/analysis , Flame Retardants/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Air Pollution/statistics & numerical data , Antarctic Regions , Environmental Monitoring , Halogenated Diphenyl Ethers/analysis , Oceans and Seas , Water Pollution, Chemical/statistics & numerical data
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