Application of GC-MS/MS for the analysis of PCDD/Fs in sewage effluents

The application of high resolution gas chromatography in combination with tandem mass spectrometry in an ion trap was tested to substitute the expensive high resolution mass spectrometry in analysing polychlorinated dibenzo-p-dioxins and furans in sewage effluents. In tandem mass spectrometry, a set of parameters has to be optimised in order to attain the required sensitivity. To the best of our knowledge, this is the first time a method development for analysing PCDD/Fs with GC-MS/MS in an ion trap is described in this detail. Nine parameters are varied, including isolation window, collision induced dissociation (CID) amplitude, CID time, acquisition mass range, broadband amplitude, CID bandwidth, modulation range, filament current and ion trap temperature. This technique can be adapted to other analytes. By this optimisation, limits of detection of 0.01-0.05 ng/l are obtained. With its selectivity and sensitivity, tandem mass spectrometry is a powerful tool for the determination of PCDD/Fs in water samples. 55 sewage effluent samples from Germany were analysed.     

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part I: PCBs in surface and deep-sea dwelling fish of the north and south Atlantic and the Monterey Bay Canyon (California)

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from upper water layers (0-200 m) to the deepwater region (> 800 m) in terms of the contamination of the biophase in both water layers. The contents of persistent organochlorine compounds like polychlorinated biphenyls (PCBs) in fish living in the upper water layers of the North Atlantic and the South Atlantic, and at the continental shelf of California (Marine Sanctuary Monterey Bay and its deep-sea Canyon) are compared to the levels in deep-sea or bottom dwelling fish within the same geographic area. The deep-sea biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs--in this case the PCBs--in the biophase of the abyss as well. It can be concluded that the bio- and geo phase of the deep-sea may act similarly as the upper horizons of forest and grasslands on the continents as an ultimate global sink for POPs in the marine environment.     

The effect of ozone on pollen development in Lolium perenne L

Perennial ryegrass plants (Lolium perenne L.) were exposed in "Closed-Top Chambers" to different ozone concentrations and to charcoal filtered ambient air to study the effect of ozone on the development of pollen. Ozone at ambient (65 nl l(-1), 8h) and elevated (110 nl l(-1), 4h) concentrations affected the maturing of pollen by inhibiting starch accumulation in pollen throughout the anther. Affected pollen persisted in the vacuolated state while normal pollen in the same anther were filled with amyloplasts. The percentage of underdeveloped pollen-determined in transversal sections-was significantly higher in exposed plants than in plants grown in filtered air. Results indicate that ozone stress was responsible for the disrupted development of pollen in L. perenne.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Translocation of metals and its effects in the tomato plants grown on various amendments of tannery waste: evidence for involvement of antioxidants

A field experiment was conducted to study the effect of different amendments of tannery sludge on physiological and biochemical parameters of tomato plant (Lycopersicon esculentum L. Mill). The accumulation of metals (Cr, Fe) in different parts of tomato plants grown on tannery sludge amended soil increased in a concentration and duration-dependent manner. The accumulation of both the metals was found lowest in the fruits of the plant. The statistical analysis of the results showed an increase in chlorophyll and protein contents in lower sludge amendment ratio at all exposures followed by a decrease at highest (100%) sludge amendment ratio. Lipid peroxidation enhanced in both root and leaves of sludge grown plants of tomato at all the sludge amendments and exposure periods, which is evidenced by increased malondialdehyde content, however the maximum increase was found in the roots (43.63%) and leaves (56.66%) of the plant grown on 100% tannery sludge at 60 d, over respective controls. The level of antioxidants, cysteine, non-protein thiol and ascorbic acid increased in the sludge grown plants of tomato to cope up with stress induced by the excess amount of the heavy metals present in the tannery sludge. The maximum increase was found in cysteine content (75.53% in the leaves), non-protein thiol content (92.68% in the roots) and ascorbic acid content (29.66% in the roots) of the plant at 75% tannery sludge after 30 d. The tomato plants were found well adopted for minimizing damage induced by reactive oxygen species, when grown on tannery sludge amendments in the present study.     

Monitoring of toxicity during degradation of selected pesticides using ionizing radiation

The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.     

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in the atmosphere and bulk deposition in Kyoto, Japan

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in atmosphere, bulk atmospheric deposition and soil in Kyoto, which is an urban city in Japan, were measured. Decabromodiphenyl ether (D(10)BDE, BDE-209) was detected in relatively high concentrations compared to other PBDE congeners in most samples. Similar results, in which D(10)BDE was predominantly detected, were reported in other studies in Japan. However, these homologue profiles differ from those of studies conducted in North America. The partitioning of semivolatile organic compounds between atmospheric gas phase and particulate-associated phase is an important factor in their environmental behavior. In this study, atmospheric particulate phase fraction (f(P)) of the brominated compounds increased with increasing bromine number, and f(P) was higher in samples collected in winter than in those collected in summer. Moreover, f(P) of PBDFs and MoBPXDFs was higher than that of PCDFs with the same halogen number. These results agree well with expectations from the vapor pressure of the brominated compounds and PCDD/Fs. Among the brominated compounds in the atmosphere, the level of MoBPXDD/Fs correlates positively with that of PCDD/Fs. This relationship has been previously observed in waste incineration samples. These results suggest that one of the sources of MoBPXDD/Fs in the atmosphere is incineration byproduct. The level of PBDD/Fs seems to correlate positively with that of PBDEs. This relationship suggest that the PBDD/Fs in the atmosphere relate to PBDEs, which is an impurity of PBDE products, or formed by the manufacture or combustion of plastics containing PBDEs.     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30 degrees F), "black" and "white" smokers, and a new-technology vehicle (tested at 72 degrees F). Diesel vehicles included current-technology vehicles (tested at 72 and 30 degrees F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.     

Comparison of various advanced oxidation processes and chemical treatment methods for COD and color removal from a polyester and acetate fiber dyeing effluent

In this paper, a comparison of various advanced oxidation processes (O3, O3/UV, H2O2/UV, O3/H2O2/UV, Fe2+/H2O2) and chemical treatment methods using Al2(SO4)3.18H2O, FeCl3 and FeSO4 for the chemical oxygen demand (COD) and color removal from a polyester and acetate fiber dyeing effluent is undertaken. Advanced oxidation processes (AOPs) showed a superior performance compared to conventional chemical treatment, which maximum achievable color and COD removal for the textile effluent used in this study was 50% and 60%, respectively. Although O3/H2O2/UV combination among other AOPs methods studied in this paper was found to give the best result (99% removal for COD and 96% removal for color), use of Fe2+/H2O2 seems to show a satisfactory COD and color removal performance and to be economically more viable choice for the acetate and polyester fiber dyeing effluent on the basis of 90% removal.