Degradation dynamics,residues and risk assessment of Dufulin enantiomers in corn plants and corn by LC/MS/MS

ABSTRACT

The degradation dynamics and terminal residues of dufulin enantiomers were investigated in two typical corn plants. A convenient and precise chiral method by high-performance liquid chromatography coupled with tandem triple quadrupole mass spectrometry (HPLC/MS/MS) using a Chiralpak IC column was developed and validated for measuring dufulin enantiomers in corn plants and corn. The two enantiomers of dufulin quickly dissipated in the corn plant, and no noticeable stereoselectivity was observed during degradation or in the final residues. After 30% rac-dufulin wettable powder with a 1- to 1.5-fold dose of the recommended value was sprayed two to three times on corn plants, the residue levels of S-(+)-dufulin and R-(-)-dufulin in corn from both sites were lower than or equal to 0.0520 mg kg^–1 on days 7, 14 and 21 after the last application. The dietary risk assessment indicated that dufulin did not exhibit obvious dietary health risks in corn samples when good agricultural practices were implemented. The findings from this study may be used to better understand the chiral profiles of dufulin in the environment and the effect of dufulin residues in corn on health.     

Toxicity of fipronil and its enantiomers to marine and freshwater non-targets

Fipronil is a phenylpyrazole insecticide used in agricultural and domestic settings for controlling various insect pests in crops, lawns, and residential structures. Fipronil is chiral; however, it is released into the environment as a racemic mixture of two enantiomers. In this study, the acute toxicity of the (S,+) and (R,-) enantiomers and the racemic mixture of fipronil were assessed using Simulium vittatum IS-7 (black fly), Xenopus laevis (African clawed frog), Procambarus clarkii (crayfish), Palaemonetes pugio (grass shrimp), Mercenaria mercenaria (hardshell clam), and Dunaliella tertiolecta (phytoplankton). Results showed that S. vittatum IS-7 was the most sensitive freshwater species to the racemic mixture of fipronil (LC50 = 0.65 microg/L) while P. pugio was the most sensitive marine species (LC50 = 0.32 microg/L). Procambarus clarkii were significantly more sensitive to the (S,+) enantiomer while larval P. pugio were significantly more sensitive to the (R,-) enantiomer. Enantioselective toxicity was not observed in the other organisms tested. Increased mortality and minimal recovery was observed in all species tested for recovery from fipronil exposure. These results indicate that the most toxic isomer of fipronil is organism-specific and that enantioselective toxicity may be more common in crustaceans than in other aquatic organisms.     

Crystal structure analysis of enantiomerically pure (+) and (-) beta-hexabromocyclododecanes

The molecular structures of individual HBCD stereoisomers are not elucidated yet. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and tentatively assigned their relative configurations. Herein we report on the isolation of enantiomerically pure (+) and (-) beta-HBCDs, both obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations determined from X-ray diffraction analysis. The absolute configuration of (+) beta-HBCD was found to be (1S,2S,5S,6R,9S,10R), while the one of (-) beta-HBCD was assigned to (1R,2R,5R,6S,9R,10S). The given structural information allows, for the first time, the unambiguous identification of these two important HBCD stereoisomers, which are typically found in technical products at proportions of about 3-5% for each enantiomer.     

Sulfur Concentrations in Plant Foliage and Related Effects

Sulfur Is an essential element for plants and is normally taken up from soil In the sulfate form. S0₂ absorbed from the air also can supply S for plant nutrition. Plants are therefore dependent on an optimum S content, but deficiencies or excesses can result in deleterious effects. The Phytotoxicology Section has conducted numerous assessment surveys in rural, urban, or industrial locations in Ontario to determine the concentrations of S in plants and related effects. During the ten year period, 1968 to 1977, about 50,000 samples of vegetation and soil were collected and analyzed for S concentrations. The results of these analyses were examined with respect to natural background concentrations of S in foliage of 33 different species, and effects observed on plant life associated with excess concentrations of S. For example, in one situation 0.35% sulfur in foliage of trembling aspen trees was found to be the threshold level for injury to occur. Some of the industries surveyed for the degree and extent of S effects in their vicinity included pulp mills, power plants, iron concentrators, and gold, nickel, and copper smelters. In interpreting the results of S analyses in plant foliage for diagnostic purposes, consideration should be given also to the geographical location, the stage of growth of the plant, the relation of visible injuries to pollutant or biological causes, the S content of the soil, and S0₂ emission data for the area.     

Hydrogen sulfide ameliorates lead-induced morphological, photosynthetic, oxidative damages and biochemical changes in cotton

Poisonous lead (Pb), among heavy metals, is a potential pollutant that readily accumulates in soils and thus adversely affects physiological processes in plants. We have evaluated how exogenous H₂S affects cotton plant physiological attributes and Pb uptake under Pb stress thereby understanding the role of H₂S in physiological processes in plants. Two concentrations (0 and 200 μM) of H₂S donor sodium hydrosulfide (NaHS) were experimented on cotton plants under Pb stress (0, 50, and 100 μM). Results have shown that Pb stress decreased plant growth, chlorophyll contents, SPAD value, photosynthesis, antioxidant activity. On the other hand, Pb stress increased the level of malondialdehyde (MDA), electrolyte leakage (EL), and production of H₂O₂ and uptake of Pb contents in all three parts of plant, viz. root, stem, and leaf. Application of H₂S slightly increased plant growth, chlorophyll contents, SPAD value, photosynthesis, and antioxidant activity as compared to control. Hydrogen sulfide supply alleviated the toxic effects of lead on plant growth, chlorophyll contents, SPAD value, photosynthesis, and antioxidant activity in cotton plants. Hydrogen sulfide also reduced MDA, EL, and production of H₂O₂ and endogenous Pb levels in the three mentioned plant parts. On the basis of our results, we conclude that H₂S has promotive effects which could improve plant survival under Pb stress.     

Investigation on gene transfer from genetically modified corn (Zea mays L.) plants to soil bacteria

Knowledge about the prevalence and diversity of antibiotic resistance genes in soil bacteria communities is required to evaluate the possibility and ecological consequences of the transfer of these genes carried by genetically modified (GM) plants to soil bacteria. The neomycin phosphotransferase gene (nptII) conferring resistance to kanamycin and neomycin is one of the antibiotic resistance genes commonly present in GM plants. In this study, we investigated kanamycin-resistant (Km(R)) and neomycin-resistant (Nm(R)) soil bacterial populations in a 3-year field trial using a commercial GM corn (Zea mays L.) carrying the nptII gene and its near isogenic line. The results showed that a portion (2.3 - 15.6 %) of cultivable soil bacteria was naturally resistant to kanamycin or neomycin. However, no significant difference in the population level of Km(R) or Nm(R) soil bacteria was observed between the GM and non-GM corn fields. The nptII gene was not detected in any of the total 3000 Km(R) or Nm(R) isolates screened by PCR. Further, total soil bacterial cells were collected through Nycodenz gradient centrifugation and bacterial community DNA was subjected to PCR. Detection limit was about 500 cells per gram of fresh soil. Our study suggests that the nptII gene was relatively rare in the soil bacterial populations and there was no evidence of gene transfer from a GM corn plant to soil bacteria based on the data from total soil bacterial communities.     

The fate of the recombinant DNA in corn during composting

In order to make regulations that safeguard food and the environment, an understanding of the fate oftransgenes from genetically modified (GM) plants is of crucial importance. A compost experiment including mature transgenic corn plants and seeds of event Bt 176 (Zea mays L.) was conducted to trace the fate of the transgene cryIA(b) during the period of composting. In bin 1, shredded corn plants including seeds were composted above a layer of cow manure and samples from the corn layer were collected at intervals during a 12-month period. The samples were tested for the transgene persistence and microbial counts and also the compost was monitored for temperature. In bin 2, piles of corn seeds, surrounded by sheep manure and straw, were composted for 12 months. A method combining nested polymerase chain reaction (PCR) and southern hybridization was developed for detection of the transgene in compost. The detection sensitivity was 200 copies of the transgene per gram of dry composted corn material. Composting commenced on day 0, and the transgene was detected in specimens from bin 1 on days 0 and 7 but not on day 14 or thereafter. The transgene in corn seeds was not detectable after 12 months of composting in bin 2. Temperatures in both bins rose to about 50 degrees C within 2 weeks and remained above that temperature for about 3 months, even when the ambient temperature dropped below -20 degrees C. Extracts from compost were inoculated onto culture plates and then were incubated at 23 to 55 degrees C. Within the first 2 weeks of composting in bin 1, the counts of bacteria incubated at 55 degrees C increased from 3.5 to 7.5 log10, whereas those incubated at 23 degrees C remained at about 7.5 log10. The counts of fungi incubated at 45 degrees C increased slightly from 2.5 to 3.1 log10, but those incubated at 23 degrees C decreased from 6.3 to 3.0 log10. The rapid degradation of the transgene during composting of Bt corn plants suggested that the composting process could be used for safe disposal of transgenic plant wastes.     

Effects of oxidants on soybean growth and yield in the Pakistan Punjab.

Plants of soybean (Glycine max L.) were grown with and without the ozone protectant EDU (N-[2-(2-oxo-1-imidazolidinyl)ethyl]-n2 phenylurea) at a suburban site, a remote rural site and a rural roadside site around the city of Lahore, Pakistan. The development and yield of the plants was determined in two experiments--one immediately post-monsoon and one in the following spring (pre-monsoon). Concentrations of nitrogen dioxide and photochemical oxidants were measured at each site. The effect on yield of EDU at the suburban site (47 and 113% increase in seed weight per plant relative to the untreated plants in the post- and pre-monsoon experiments, respectively) was similar to the effects of filtration on yield on soybean in a parallel open-top chamber study at the same site (77% increase relative to plants subjected to unfiltered air for the pre-monsoon experiment). Effects of EDU on yield were greater at both rural sites than at the suburban site in both experiments, and greater in the spring experiment (182% at the remote rural site and 285% at the rural roadside site) than in the post-monsoon experiment (94% at the remote rural site and 170% at the rural roadside site); oxidant concentrations were also greater at the rural sites than at the suburban site, and greater in the spring experiment than the post-monsoon experiment. The results imply that ozone may be causing significant crop losses in rural areas around Lahore; however, the geographical extent of the problem, and the implications for peri-urban agriculture around other cities of south Asia are uncertain.     

The arbuscular mycorrhizal fungus Glomus mosseae induces growth and metal accumulation changes in Cannabis sativa L

The effect of arbuscular mycorrhiza on heavy metal uptake and translocation was investigated in Cannabis sativa. Hemp was grown in the presence and absence of 100 microg g-1 Cd and Ni and 300 microg g-1 Cr(VI), and inoculated or not with the arbuscular mycorrhizal fungus Glomus mosseae. In our experimental condition, hemp growth was reduced in inoculated plants and the reduction was related to the degree of mycorrhization. The percentage of mycorrhizal colonisation was 42% and 9% in plants grown in non-contaminated and contaminated soil, suggesting a significant negative effect of high metal concentrations on plant infection by G. mosseae. Soil pH, metal bioavailability and plant metal uptake were not influenced by mycorrhization. The organ metal concentrations were not statistically different between inoculated and non-inoculated plants, apart from Ni which concentration was significantly higher in stem and leaf of inoculated plants grown in contaminated soil. The distribution of absorbed metals inside plant was related to the soil heavy metal concentrations: in plant grown in non-contaminated soil the greater part of absorbed Cr and Ni was found in shoots and no significant difference was determined between inoculated and non-inoculated plants. On the contrary, plants grown in artificially contaminated soil accumulated most metal in root organ. In this soil, mycorrhization significantly enhanced the translocation of all the three metals from root to shoot. The possibility to increase metal accumulation in shoot is very interesting for phytoextraction purpose, since most high producing biomass plants, such as non-mycorrhized hemp, retain most heavy metals in roots, limiting their application.     

Effects of rhizobium, arbuscular mycorrhizal fungi and anion content of simulated rain on subterranean clover

An experiment was conducted to determine the extent to which rhizobia, mycorrhizal fungi, and anions in simulated rain affect plant growth response to acid deposition. Germinating subterranean clover seeds were planted in steam-pasteurized soil in pots and inoculated with Rhizobium leguminosarum, Glomus intraradices, Glomus etunicatum, R. leguminosarum + G. intraradices, R. leguminosarum + G. etunicatum, or no microbial symbionts. Beginning 3 weeks later, plants and the soil surface were exposed to simulated rain in a greenhouse on 3 days week(-1) for 12 weeks. Rain solutions were deionized water amended with background ions only (pH 5.0) or also adjusted to pH 3.0 with HNO3 only, H2SO4 only, or a 50/50 mixture of the two acids. Glomus intraradices colonized plant roots poorly, and G. intraradices-inoculated plants responded like nonmycorrhizal plants to rhizobia and rain treatments. Variation in plant biomass attributable to different rain formulations was strongest for G. etunicatum-inoculated plants, and the effect of rain formulation differed with respect to nodulation by rhizobia. The smallest plants at the end of the experiment were noninoculated plants exposed to rains (0.38 g mean dry weight total for 3 plants pot(-1)). Among nonnodulated plants infected by G. etunicatum, those exposed to HNO3 rain were largest, followed by plants exposed to HNO3 + H2SO4, pH 5.0, and H2SO4 rain, in that order. Among plants inoculated with both R. leguminosarum + G. etunicatum, however, the greatest biomass occurred with pH 5.0 rains, resulting in the largest plants in the study (1.00 g/3 plants). Treatment-related variation among root and shoot biomass data reflected those for whole-plant biomass. Based on quantification of biomass and N concentrations in shoot and root tissues, total N content of plants inoculated with G. etunicatum alone and exposed to the HNO3 + H2SO4 rains was approximately the same as plants inoculated with R. leguminosarum + G. entunicatum and exposed to pH 5 rains. Thus, the acid-mixture rains and rhizobia under no acid deposition provided approximately equal amounts of N in biomass. The significant interactions among rain formulation and the symbiotic status of the plants suggest that conclusions concerning the impact of acid deposition on plants in the environment cannot be considered reliable because most experiments on which such assessments are based have not tested confounding influences of microorganisms and precipitation characteristics.     

The Fate of the Recombinant DNA in Corn During Composting

Abstract

In order to make regulations that safeguard food and the environment, an understanding of the fate of transgenes from genetically modified (GM) plants is of crucial importance. A compost experiment including mature transgenic corn plants and seeds of event Bt 176 (Zea mays L.) was conducted to trace the fate of the transgene cryIA(b) during the period of composting. In bin 1, shredded corn plants including seeds were composted above a layer of cow manure and samples from the corn layer were collected at intervals during a 12-month period. The samples were tested for the transgene persistence and microbial counts and also the compost was monitored for temperature. In bin 2, piles of corn seeds, surrounded by sheep manure and straw, were composted for 12 months. A method combining nested polymerase chain reaction (PCR) and southern hybridization was developed for detection of the transgene in compost. The detection sensitivity was 200 copies of the transgene per gram of dry composted corn material. Composting commenced on day 0, and the transgene was detected in specimens from bin 1 on days 0 and 7 but not on day 14 or thereafter. The transgene in corn seeds was not detectable after 12 months of composting in bin 2. Temperatures in both bins rose to about 50°C within 2 weeks and remained above that temperature for about 3 months, even when the ambient temperature dropped below ?20°C. Extracts from compost were inoculated onto culture plates and then were incubated at 23 to 55°C. Within the first 2 weeks of composting in bin 1, the counts of bacteria incubated at 55°C increased from 3.5 to 7.5 log ₁₀, whereas those incubated at 23°C remained at about 7.5 log ₁₀. The counts of fungi incubated at 45°C increased slightly from 2.5 to 3.1 log₁₀, but those incubated at 23°C decreased from 6.3 to 3.0 log ₁₀. The rapid degradation of the transgene during composting of Bt corn plants suggested that the composting process could be used for safe disposal of transgenic plant wastes.     

Crystal structure of δ-isobutoxypentabromo-cyclododecanes, kinetics and selectivity of their isomerization during thermal treatment of flame-proofed polystyrenes

Hexabromocyclododecanes (HBCDs) are persistent organic pollutants now ubiquitous in the environment. Technical HBCD mixtures and with it flame-proofed polystyrenes (FP-PS) also contain isobutoxypentabromocyclododecanes (iBPBCDs) as minor constituents, which are possibly released together with HBCDs. So far, eight diastereomeric pairs of enantiomers named as α-, β-, γ-, δ-, ?-, ξ-, η-, and θ-iBPBCDs with proportions of 10%, 5%, 2%, 21%, 11%, 11%, 12% and 28% were found in technical HBCD. Herein the crystal structure of racemic δ-iBPBCD, the second most prominent diastereomer, is presented and assigned to (1S)-1-isobutoxy-(2R,5R,6S,9S,10S)-2,5,6,9,10-pentabromocyclododecane and its enantiomer. During thermal treatment of FP-PS, e.g. the production of extruded polystyrenes (XPS), proportions of δ-iBPBCDs decrease and those of other stereoisomers increase. Evidence was found that δ-iBPBCDs isomerize stereo- and regioselectively to β-iBPBCDs. Based on structural and kinetic data, a transformation mechanism was proposed. Apparent first-order rate constants (k_iso) of 0.0019, 0.0050, and 0.012 min⁻¹ are found for the δ- to β-iBPBCD isomerization at 120, 130, and 140 °C, respectively, corresponding to half-lives of 360, 140, and 56 min. These transformations also occur during the production of XPS, which predominantly contain β-iBPBCDs, whereas δ-iBPBCDs dominate in materials experiencing lower thermal stress, e.g. expanded polystyrenes (EPS). The relative configurations of δ- and θ-iBPBCDs are TtCtCt, like the one of γ-HBCDs. γ-HBCDs are the kinetically and α-HBCDs with a TcCtCc configuration the thermodynamically favored products. In analogy, β-iBPBCDs are assumed to have a TcCtCc configuration like α-HBCDs because they are formed from δ-iBPBCDs under thermodynamic control. In conclusion, HBCD- and iBPBCD-patterns in flame-proofed polystyrenes vary substantially, reflecting the thermal stress these materials have experienced. When released to the environment, these patterns might further change, as observed for HBCDs.     

Enhanced phytoextraction of Cu, Pb, Zn and Cd with EDTA and EDDS

Chemically enhanced phytoextraction has been proposed as an effective approach to removing heavy metals from contaminated soil through the use of high biomass plants. Using pot experiments, the effects of the application of EDTA, EDDS and citric acid on the uptake of Cu, Pb, Zn and Cd by corn (Zea mays L. cv. Nongda 108) and bean (Phaseolus vulgaris L. white bean) plants were studied. The results showed that EDDS was more effective than EDTA at increasing the concentration of Cu in corn and beans. The application of 5 mmol kg-1 soil EDDS to soil significantly increased concentrations of Cu in shoots, with maximum levels of 2060 and 5130 mg kg-1 DW in corn and beans, respectively, which were 45- and 135-fold higher than that in the corresponding control plants to which chelate had not been applied. Concentrations of Zn in shoots were also higher in the plants treated with EDDS than in those treated with EDTA. For Pb and Cd, EDDS was less effective than EDTA. The maximum Cu phytoextraction was found with the EDDS treatment. The application of EDTA and EDDS also significantly increased the shoot-to-root ratios of the concentrations of Cu, Pb, Zn and Cd in both plant species. The results of metal extraction with chelates showed that EDDS was more efficient at solubilizing Cu and Zn than EDTA, and that EDTA was better at solubilizing Pb and Cd than EDDS.     

2,5,6,9,10-Pentabromocyclododecanols (PBCDOHs): a new class of HBCD transformation products

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C₁₈-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials.     

Growth and foliar nitrogen status of four plant species exposed to atmospheric ammonia

A chamber study was conducted to evaluate the growth response and leaf nitrogen (N) status of four plant species exposed to continuous ammonia (NH3) for 12 weeks (wk). This was intended to evaluate appropriate plant species that could be used to trap discharged NH3 from the exhaust fans in poultry feeding operations before moving off-site. Two hundred and forty bare-root plants of four species (Juniperus virginiana (red cedar), Gleditsia triacanthos var. inermis (thornless honey locust), Populus sp. (hybrid poplar), and Phalaris arundinacea (reed canary grass) were transplanted into 4- or 8-L polyethylene pots and grown in four environmentally controlled chambers. Plants placed in two of the four chambers received continuous exposure to anhydrous NH3 at 4 to 5 ppm while plants in another two chambers received no NH3. In each of the four chambers, 2 to 4 plants per species received no fertilizer while the rest of the plants were fertilized with a 100 ppm solution containing 21% N, 7% phosphorus, and 7% potassium. The results showed that honey locust was the fastest-growing species. The superior growth of honey locust among all species was also supported by its total biomass, root, and root dry matter (DM) weights. For all species there was a trend for plants exposed to NH3 to have greater leaf DM than their non-exposed counterparts at 6 (43.0 vs. 30.8%; P = 0.09) and 12 wk (47.9 vs. 36.6%; P = 0.07), and significantly greater (P 相似文献   

Absorption, balance and metabolism of C-2, 4, 6-trichlorophenol in hydroponic tomato plants

Most of the 2, 4, 6-TCP applied in the nutrient solution of the hydroculture test was volatilised; a proportion was absorbed by the developed plant roots and to a small extent isomerised. Significant portions of the non-extractable tomato plant residues were found in the isolated lignin and cellulose fractions.     

Detached leaf culture: viability to evaluate 2,4-D toxicity symptoms in cotton apex leaves

To study the viability of detached leaf culture technique, studies were carried out with detached leaves from cotton apex (true trilobed leaves). The prepared leaves were sprayed with 2,4-D amine and ester, at rates of 10, 30, 70, and 100% of the recommended doses. Detached leaves without herbicide spray were used as controls. Simultaneously, a greenhouse experiment was conducted with the same treatments as used for the detached leaves experiment. Toxicity was measured through a 0-to-5 grading according to the percentage of affected leaf area in the detached leaves experiment or examining the affected rate of whole plant as indicated in the greenhouse. Results showed that the ester form of the herbicide induced earlier and more severe toxicity symptoms in detached leaves and greenhouse grown plants. Positive and significant correlations (p < 0.001) were found between toxicity results obtained at 7 and 14 days after application in detached leaves and greenhouse plants (r = 0.97 and 0.92, respectively). Negative, significant correlations (p < 0.005) were found between the toxicity levels found at 7 and 14 days after application in detached leaves and dry matter of cotton plants grown in the greenhouse (r= - 0.92 and -0.92, respectively).     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack flue gases of sinter plants

This study investigated four sinter plants, classified into two categories--with selective catalytic reduction (SCR) (S1, S2 and S3) and without SCR (S4) as its air pollution control device. Polychlorinated dibenzofurans (PCDFs) are dominant in the stack flue gases of sinter plants with and without SCR. The polychlorinated dibenzofurans/polychlorinated dibenzo-p-dioxins (PCDFs/PCDDs) ratio exceeds 1 extremely. The degree of chlorination of the sinter plant without SCR is towards hepta and hexa congeners while that of the sinter plant with SCR is towards penta and hexa congeners. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) and not only reduced in degree of chlorination. The overall concentration in the stack flue gas of sinter plants with SCR (7.97-14.1 ng/Nm(3); 0.995-2.06 ng TEQ/Nm(3)) is lower than that of the sinter plant without SCR (28.9 ng/Nm(3); 3.10 ng TEQ/Nm(3)). In Taiwan, based on the emission factors of 0.970 microg TEQ/ton-feedstock (sinter plants with SCR) and 3.13 microg TEQ/ton-feedstock (sinter plant without SCR), the annual PCDD/F emission of 44.7 g TEQ/year from sinter plants is 60 and 121 times higher than those from municipal solid waste incinerators (0.750 g TEQ/year) and MWIs (0.369 g TEQ/year). These results show that sinter plants have become the dominating PCDD/F emission source since tighter emission limits have been applied to incinerators.     

Comparative study of methodologies for the analysis of PCDDs and PDCFs in powdered full-fat milk. PCB, PCDD and PCDF levels in commercial samples from Spain

Feasibility of two different extraction methods involving solid-liquid extraction and Soxhlet extraction, previously used for the determination of lipid contents and PCB levels on powdered full-fat milk, are now examined for simultaneous PCDD/F analysis. The results of this study are consistent with those found for PCBs. The solid-liquid procedure provides the most efficient extraction of both labelled spiked and endogenous PCDD/Fs with the lowest variability. The average recoveries were 101% (R.S.D. = 6.9%) for 13C12-2,3,7,8-TCDD and 95% (R.S.D. = 11%) for 13C12-1,2,3,4,7,8-HxCDD. The R.S.D.s for endogenous 2,3,7,8-PCDD/Fs were in the 9.3-25% range. In addition, this methodology simplified the subsequent clean-up step as it allowed a semi-selective extraction of the apolar lipids from the milk. The proposed method was applied to simultaneous PCB and PCDD/F analyses in different brands of powdered full-fat milks commercially available in Spain. In all cases, very similar PCB and PCDD/F levels were found. Differences among batches from the same manufacturer were even lower. The total i-TEQ average for PCDDs and PCDFs in the 22 powdered full-fat milk samples analysed was 1.87 pg/g fat basis. This value was similar to those found in cow's milk from other European countries.