Altitudinal distributions of BDE-209 and other polybromodiphenyl ethers in high mountain lakes

The present study shows the occurrence of 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) in microbial biofilms of Pyrenean and Tatra high mountain lakes despite its low vapor pressure and high hydrophobicity. Aerosol air transport is therefore a feasible mechanism for BDE-209 accumulation in sites up to 2688 m above sea level. This compound and other PBDEs exhibit altitudinally-dependent distribution involving higher concentrations with increasing mountain lake elevation. However, the apparently very high enthalpies of the concentration gradients observed, including BDE-209, suggest that bacterial anaerobic debromination also plays a significant role in the resulting altitudinal distributions. This microbial mechanism explains the relative abundances of PBDEs and their within lake differences between rocky and sediment microbial biofilms, thereby showing that the altitudinal pattern observed is not purely due to water temperature control on bacterial activity but also to changes in the availability of anaerobic microenvironments which increase with increasing lake productivity at lower altitudes.     

Study of the enantioselective elimination of four toxaphene congeners in rat after intravenous administration by high resolution gas chromatography negative ion mass spectrometry

This study was performed to investigate the possible enantioselective metabolism of the four chlorinated bornanes: #26, #32, #50 and #62 (according to the Parlar nomenclature) by rats. Rats were exposed to a mixture of these toxaphenes by a single intravenous injection. Enantiomer ratios (ER) as well as the enantiomer fractions (EF) were determined in brain, adipose tissue and liver samples at six time intervals by high resolution gas chromatography (HRGC) coupled to negative ion chemical ionization (NICI) mass spectrometry (MS). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Significant time-dependent changes of ER and EF were found in all the three tissues for #26, #50 and #62. Greatest deviations from racemic composition were found in the liver, which is known to be the major metabolizing organ for toxaphenes. #32 was metabolized the fastest, but showed no changes in ER. Brief information is also included about the possible reasons for the different behaviors of the four congeners in the studied tissues.     

Occurrence and formation of trihalomethanes in marine aquaria studied using solid-phase microextraction gas chromatography-mass spectrometry

The occurrence and formation of chlorinated and brominated trihalomethanes (THMs) were studied in artificial saltwater and natural seawater marine aquaria as well as in groundwater and surface waters. A new headspace solid-phase microextraction method was used, which included gas chromatography-mass spectrometry and provided method detection limits of less than 0.1 microg/L, with a signal-to-noise ratio of 3 to 5. The results showed that disinfection by using either chlorine or ozone caused a significant formation of THMs in situ. Speciation of the THMs was a strong function of the water matrix, with initial bromide concentrations playing a pivotal role. These results provide a tool for understanding and monitoring the formation of key disinfection byproducts in marine aquaria that may cause respiratory, eye irritation, or other health concerns.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

固相萃取—气相色谱质谱法测定水样中的毒死蜱及其代谢产物

建立了水样中毒死蜱及其主要代谢产物3,5,6-三氯吡啶醇(TCP)的固相萃取—气相色谱质谱检测法,即采用固相萃取对水样中的毒死蜱及其代谢产物TCP进行富集,浓缩后经双(三甲基硅烷基)三氯乙酰胺(BSTFA)衍生TCP,采用气相色谱质谱进行测定。同时,采用外标法对毒死蜱和TCP进行定量。结果表明,该方法的线性范围为20~1 000μg/L,毒死蜱和TCP的检出限分别为0.375、0.100μg/L;环境水样中的毒死蜱和TCP平均加标回收率分别为89.12%~93.44%和87.37%~90.75%,相对标准偏差(RSD)为2.79%~6.64%和1.22%~5.48%。     

Measurement of trihalomethanes in potable and recreational waters using solid phase micro extraction with gas chromatography-mass spectrometry

Solid phase micro extraction (SPME) was applied to the determination of selected trihalomethanes (THMs), chloroform, bromodichloromethane, dibromochloromethane, bromoform, in potable and recreational waters. The selected samples were environmentally significant due to mandatory limits imposed by regulatory agencies. Extraction of the analytes was performed using headspace SPME (fused silica fibre with a 100 microm poly(dimethylsiloxane coating) followed by thermal desorption at 220 degrees C and GC-MS analysis. A linear working range of 10-160 microg/l was established with relative standard deviations (%RSD) within the range, 0.9-19%. Limits of detection (LOD) were 1.0-2.8 microg/l. The highest THM concentration was 61.8 microg/l which was well within the proposed European Union directive of 100 microg/l. The total THMs determined in swimming pool waters ranged from 105-134 microg/l, with chloroform accounting for 84-86% of total THM.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 1. Bioaccumulation and elimination kinetics of individual congeners and their debrominated metabolites

The uptake and elimination of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, then depurated over a five-month period. The results show that all of the studied PBDEs accumulate in fish tissues, including the higher brominated congener BDE-209. Several additional PBDE congeners were identified in the tissues of exposed fish, revealing PBDE transformation, mainly via debromination. The identified congeners originating from PBDE debromination include BDE-49 and BDE-202 and a series of unidentified tetra-, penta-, and hepta- BDEs. Contaminant assimilation efficiencies (AEs) were related to their hydrophobicity (log K_ow) and influenced by PBDE biotransformation. Metabolism via debromination appears to be a major degradation route of PBDEs in juvenile sole in comparison to biotransformation into hydroxylated metabolites.     

Incidence of polybrominated diphenyl ethers in central air conditioner filter dust from a new office building

This study examined polybrominated diphenyl ethers (PBDEs) in central air conditioner filter (CACF) dust from a new office building in Shenzhen, China. Human exposure to PBDE via dust inhalation and ingestion were also estimated. PBDEs level in CACF dust was lower than those in the other countries and regions. Approximately 0.671 pg/kg bw/day PM_2.5 (Particulate Matter up to 2.5 μm in size) bounded Σ₁₅PBDEs can be inhaled deep into the lungs and 4.123 pg/kg bw/day PM₁₀ (Particulate Matter up to 10 μm in size) bounded Σ₁₅PBDEs tend to be deposited in the upper parts of the respiratory system. The average total intake of Σ₁₅PBDEs via dust inhalation and ingestion for adults reached ∼141 pg/kg bw/day in this building. This value was far below the reference dose (RfD) recommended by United States Environmental Protection Agency. Human exposure to PBDEs via dust inhalation and ingestion in the new building is less than the old ones.     

Polybrominated diphenyl ethers occurrence in major inflowing rivers of Lake Chaohu (China): Characteristics,potential sources and inputs to lake

Eight commonly occurring polybrominated diphenyl ethers (PBDEs), including BDE 28, 47, 99, 100, 153, 154, 183, 207, and 209, were investigated in water samples from seven major inflowing rivers of Lake Chaohu to determine the distribution characteristics, potential sources and inputs to the lake. The sum of 8 BDE congeners (Σ₈PBDEs) had a concentration varied from 0.31 to 84 ng L⁻¹, with those of BDE 209, BDE 47, BDE 99, and BDE 153 being 0.31–83, <0.012–0.36, <0.012–1.3, and <0.012–0.77 ng L⁻¹, respectively. These levels were in the high range of the global PBDEs concentrations in the water environments. The highest concentrations of Σ₈PBDEs were detected in the western rivers, of which the main pollution sources were strongly related to human activities in urban centers, such as automobile-derived wastes. A sewage treatment plant was likely an important source of the lower brominated BDEs input to one western river. The correlation analyses (all p < 0.05) between PBDEs and DOC, TN, TP, and EC, suggested that the distributions and sources of PBDEs in rivers might also be related with the soil erosion by heave floods. Σ₈PBDEs input to Lake Chaohu from the rivers outlets was estimated at 344 kg yr⁻¹ during the flood season. BDE 209 was the dominant contributor with an input of 340 kg yr⁻¹, followed by BDE 99 (1.3 kg yr⁻¹), BDE 47 (0.83 kg yr⁻¹) and BDE 153 (0.60 kg yr⁻¹).     

固相萃取-气相色谱/质谱法测定水中多环芳烃

建立了固相萃取-气相色谱／质谱联用测定水中多环芳烃(PAHs)的分析方法．优化了固相萃取条件。结果表明,固相萃取效率高、萃取时间短,采用MS的选择离子检测方式对实际水样中PAHs进行定性定量分析,平均回收率在80．4％～115％之间,相对标准偏差为7．03％～18．5％,方法的检出限在0．010～0．020μg／L之间。通过实际样品中PAHs的分析表明,该法快速,溶剂用量少,能满足痕量分析的要求。     

Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Analysis of organochlorine pesticides in water by novel activated carbon fiber-solid phase microextraction coupled with gas chromatography-mass spectrometry

This study describes a fast activated carbon fiber-solid phase microextraction (ACF-SPME) method for determining organochlorine pesticides (OCPs) in water. The pesticides in this study consist of Hexachlorobenzene (HCB) and alpha-, beta-, gamma-hexachlorocyclohexanes (HCHs). The optimal experimental procedures for the adsorption and desorption of four OCPs were evaluated. The linearity was obtained with a RSD of 20% for the OCPs studied over a range from 1.0 to 100 microg/L. The limits of detection at ng/L level were achieved with GC-MS under selected ion monitoring (SIM) acquisition mode. The proposed method was applied to the determination of OCPs concentration in tap water. The results have demonstrated the suitability of the ACF-SPME-GC-MS approach for the analysis of multi-residue OCPs in water. Compared to the commercial fiber, ACF has shown its advantages in solvent-resistance, thermal stability, and the cost. The results obtained in this study suggest that ACF is a promising choice in solid phase microextraction.     

Bioaccumulation and bioavailability of polybrominated diphynel ethers (PBDEs) in soil

Earthworms were exposed to artificially contaminated soils of DE-71 and DE-79 to investigate the bioaccumulation and bioavailability of PBDEs in soil. All major congeners were bioavailable to earthworms. The uptake and elimination rate coefficients of PBDEs decreased with their logK_ows. The biota soil accumulation factors of PBDEs also declined with logK_ow. These may be due to the large molecular size and the high affinity of PBDEs to soil particles. The concentrations extracted by Tenax for 6 h correlated very well with those found in earthworms, suggesting that the bioavailability of PBDEs in soil is related to the fraction of rapid desorption from soil. This also indicates that 6 h Tenax extraction is a good proxy for the bioavailability of PBDEs to earthworms in soil. The BSAFs of PBDEs in aged soil decreased 22-84% compared to freshly spiked soil, indicating that aging may diminish the bioavailability of PBDEs in soil significantly.     

Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg^?1, respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Suitability of a magnetic particle immunoassay for the analysis of PBDEs in Hawaiian euryhaline fish and crabs in comparison with gas chromatography/electron capture detection-ion trap mass spectrometry

A gas chromatograph/electron capture detector-ion trap mass spectrometer (GC/ECD-ITMS) was used for the determination of polybrominated diphenyl ethers (PBDEs) in euryhaline fish and crabs. GC/ECD-ITMS results showed that average recoveries from the spiked fish samples are in a range of 58-123% with relative standard deviations (RSDs) of 5-19%. PBDE concentrations obtained from GC/ECD-ITMS ranged from 28 ng/g to 1845 ng/g lipid weight (lw) in all aquatic species collected from Hawaiian brackish waters. The general BDE congener concentration profile observed in this study is BDE-47 > BDE-100 > BDE-154 > BDE-99 > BDE-153 > BDE-28 > BDE-183. The ELISA results expressed as BDE-47 equivalents correlated well with those of GC/ECD-ITMS, with a correlation coefficient (R² = 0.68) and regression coefficient (slope = 0.82). Comparison of ELISA with GC/ECD-ITMS results demonstrated that ELISA provides a timely and cost-effective method to screen PBDEs in fish and crab samples.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.