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Biomedical subjects

K W Schramm

Publications and source records attributed to K W Schramm.

At least 19 recordsLinked to original sources
PubMed2001

Emission of nonchlorinated and chlorinated aromatics in the flue gas of incineration plants during and after transient disturbances of combustion conditions: delayed emission effects.

The profiles of different products of incomplete combustion (PIC) in the flue gas of a 1 MW pilot combustion facility were investigated under normal steady-state and disturbed combustion conditions. The behavior of emission profiles after disturbed combustion conditions was investigated in order to obtain a better understanding of emission memory effects. Highly time-resolved, quantitative on-line measurements of several aromatic species down to low ppbv or higher pptv concentrations were performed by a mobile resonance-enhanced multiphoton ionization time-of-flight mass spectrometer. Conventional analytical methods (gas chromatography-mass spectrometry and high-performance liquid chromatography) were also applied for measurement of polycyclic aromatic hydrocarbons (PAH) and polychlorinated dibenzo-p-dioxins and -furans (PCDD/F). The sampling point was located in the high-temperature region of the plant at the outlet of the post-combustion chamber at temperatures between 650 and 880 degrees C, prior to any emission reduction devices. The investigation pointed out that after a short phase of disturbed combustion conditions, e.g., due to process changes, transient puffs, or malfunctions, the composition of combustion byproducts in the flue gas can be changed drastically for a very long time ("memory emission" effect). It is suggested that carbonaceous layers, deposited on the inner walls in the high-temperature zone of the plant, might be responsible for the observed memory emission of some PAH species. Drastic changes in the profiles of the PCDD/F homologues were also observed during memory emission conditions. The PAH memory most likely is due to pyrolytic degradation of the carbonaceous layers, while the altered PCDD/F homologue pattern may be mediated by the high catalytic activity of the freshly formed deposit layers. Finally, it should be emphasized that a rich pattern of aromatic species, including PCDD/F, was found in a temperature regime well above the typical temperature window (approximately 300 degrees C) for de novo PCDD/F formation.

Air Pollutants↗
PubMed2001

Application of coupled liquid chromatography-mass spectrometry in photolysis studies of the herbicide triflusulfuron-methyl.

The photochemical fate of the herbicide triflusulfuron-methyl in aqueous solution under UV light (lambda > 290 nm) was investigated. Nine photoproducts were detected and tentatively identified by LC/MS and LC/MS/MS analysis. The main routes of degradation involve the cleavage and/or contraction of the sulfonylurea bridge with the elimination of sulfur dioxide, which increases the acidity of the reaction medium. On the basis of the results obtained a photodegradation pathway is proposed.

Benzoates↗
PubMed2001

Bioaccumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans in the foodweb of Ya-Er Lake area, China.

Bioaccumulation of PCDD/F in the foodweb was investigated in the Ya-Er Lake area, which was heavily polluted by PCDD/F. The high concentrations of PCDD/F in sediment can be transferred and bioaccumulated by aquatic organisms and humans through various pathways. Benthonic invertebrate animals and aquatic plants with a lot of fibers in the root can accumulate PCDD/F from sediment and water. Snail (Bellamya aeruginosa), shrimp (Macrobranchium sp.) and freshwater mussel (Acuticosta chinensis (Lea)) took up PCDD/F from the water and maintained the emission patterns, whereas fish tended to selectively accumulate 2,3,7,8-substituted isomers. The tissues of fish-eating bird and duck (Anas platyrhynchos) were very highly contaminated by PCDD/F due to ingestion of fish and other aquatic organisms from sediment. The residual concentration in breast milk depended on the original concentration of PCDD/F in the food. A resident in Ya-Er Lake area showed a daily intake of PCDD/F of about 9.14 pg TEQ/kg body weight/day. This is higher than the tolerable daily intake (TDI) for PCDD/F (1 pg TEQ/kg body weight/day), which was recommended by the World Health Organization (WHO).

Animals↗
PubMed2001

Mobility and profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment of Ya-Er Lake, China.

The sediment of Ya-Er Lake had been heavily polluted by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from the former chloralkali industry. The total amounts of PCDD/Fs and I-TEQ decreased along the water flow direction and also decreased from top to bottom layers of sediment cores. Sediment of Pond 1 was dominated by PCDF. especially TCDF. In contrast, in the other four ponds, PCDD dominated in all layers and octachlorinated dibenzo-p-dioxin (OCDD) predominated in all of the homologues. When homologue profiles from sediments and water samples were compared using principal component analysis (PCA), the first two principal components represented 95.2% of the variance in the data. The first component explained 75.9% of the variance and the second one 19.3%. Two clusters were most distinct, presenting a shift in PCDD/Fs composition from PCDF to heptachlorinated dibenzo-p-dioxin (HpCDD) and OCDD in sediments and water from Pond I to Ponds 2-5. The pattern variation between Pond I and Ponds 2-5 in Ya-Er Lake was most likely due to the change of process in the chemical plant after the dams between the ponds were built. The results of the present study also showed that log Koc of PCDD/Fs calculated from data of sediment and water in the field were comparable with theoretical log Koc. The results also implied that the concentrations of PCDD/Fs in water and sediments could be predicted from each other by log Koc.

Benzofurans↗
PubMed2001

Quantitative structure-property relationships (QSPRs) on direct photolysis of PCDDs.

By the use of partial least squares (PLS) method and 27 quantum chemical descriptors computed by PM3 Hamiltonian, a statistically significant QSPR were obtained for direct photolysis quantum yields (Y) of selected Polychlorinated dibenzo-p-dioxins (PCDDs). The QSPR can be used for prediction. The direct photolysis quantum yields of the PCDDs are dependent on the number of chlorine atoms bonded with the parent structures, the character of the carbonoxygen bonds, and molecular polarity. Increasing bulkness and polarity of PCDDs lead to decrease of log Y values. Increasing the frontier molecular orbital energies (Elumo and Ehomo) and heat of formation (HOF) values leads to increase of log Y values.

Carbon↗
PubMed2001

Persistence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in Ya-Er Lake area, China.

The concentrations of polychlorinaxed dibenzo-p-dioxins and dibenzofurans (PCDD/F) in surface sediment, soil, human hair, and fish muscle from Ya-Er Lake area, China, were analyzed. The results showed that there were very high concentrations of PCDD/F existing in these samples. The results also indicated that Ya-Er Lake, which received a large amount of waste water from a nearby chloroalkali plant, was heavily polluted by PCDD/F. The present study demonstrated that those congeners, which possess at least three chlorine atoms in the lateral position with a fourth chlorine atom in the neighborhood bond of the third single chlorine atom, such as 1,2,7,8-TCDF and 2,3,6,7-TCDF, were very resistant to biodegradation due to the "neighbor effect" of every two chlorine atoms. The present study suggested that human hair may be a suitable alternative bioindicator for detecting PCDD/F exposure.

Animals↗
PubMed2001

Is it possible to develop a QSPR model for direct photolysis half-lives of PAHs under irradiation of sunlight?

By the use of the partial least squares method and 11 fundamental quantum chemical descriptors computed from the PM3 Hamiltonian, a Quantitative Structure-Property Relationship model was obtained for direct photolysis half-lives of selected polycyclic aromatic hydrocarbons (PAHs) under irradiation of sunlight. Direct photolysis half-lives for some other PAHs without reported values were predicted. It was concluded from the model that the main factors affecting photolysis half-lives of PAHs under irradiation of sunlight are PAH absolute hardness and electronegativity, which are related to the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital, (Elumo - Ehomo) and (Elumo + Ehomo), respectively. Increasing Ehomo and the average molecular polarizability (alpha) values of the PAHs leads to decrease of photolysis half-lives. Increasing (Elumo - Ehomo) and Elumo values of the PAHs leads to an increase of the PAH photolysis half-lives.

Environmental Pollutants↗
PubMed2000

Liver tumor-promoting activity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in TCDD-sensitive and TCDD-resistant rat strains.

Risk assessment of dioxins is currently based on induction of liver tumors in rats. The toxicity of dioxins is characterized by large sensitivity differences among animal species and even strains of the same species, which complicates the risk assessment. The significance of these differences in dioxin-induced carcinogenicity is not known. We therefore studied the liver tumor-promoting activity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the sensitive Long-Evans (L-E) and the resistant Han/Wistar (H/W) rats differing >1000-fold in their sensitivity to the acute lethaity of TCDD. Female rats were partially hepatectomized, initiated with nitrosodiethylamine, and treated with TCDD for 20 weeks. Altered hepatic foci (AHF) were stereologically quantitated using glutathione S-transferase P as a marker. AHF were significantly (P < 0.001) and dose dependently increased in L-E rats at 10 and 100 ng/kg/day, but in H/W rats only at 1000 ng/kg/day and above, indicating a remarkable (approximately 100-fold) sensitivity difference between L-E and H/W rats. The same sensitivity difference but 10-fold less foci were observed between nonhepatectomized/noninitiated L-E and H/W rats. Induction of AHF was related to hepatotoxicity but not to cytochrome P4501A1 activity in the liver. Liver TCDD concentrations were similar in both strains. H/W rats are exceptionally resistant to induction of AHF by TCDD, and the resistance is associated with an altered transactivation domain of the aryl hydrocarbon receptor. Genetic differences may account for significant interindividual/intraspecies sensitivity differences in dioxin-induced carcinogenesis. Understanding the role of transactivation domain of the aryl hydrocarbon receptor in carcinogenesis is therefore likely to improve dioxin risk assessment.

Alanine Transaminase↗
PubMed2000

Distribution, transformation, and long-term accumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of fish and piscivorous birds.

The present study monitored 10-year-old fish and piscivorous birds from sites contaminated for many years. The data reflected the results of actual, long-term environmental exposures. The results demonstrate that different tissues of fish have quite different concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). The concentration order of PCDD/F within fish is liver congruent with egg congruent with intestine>kidney congruent with heart>gill congruent with bladder>muscle>brain. The concentration order of PCDD/F within piscivorous birds was liver>egg congruent with heart>muscle congruent with stomach>brain. The results obtained also demonstrate that the accumulation patterns of piscivorous birds and fish are quite different. The tissues of fish and piscivorous birds have different capacities for bioaccumulation and biotransformation of PCDD/F; variable proportions of TEQs were also found throughout their bodies. In fish, toxic equivalency quotient (TEQ): PCDD/F ratios in various tissues ranged from 0.01 to 0.07, whereas in birds the ratios ranged from 0.07 to 0.43. If the concentrations are normalized with lipid content, the results vary less. The effect of different lipid properties is obvious in the case of brain tissue, which is richer in phospholipids.

Animals↗
PubMed2000

River sediment (S-37)--a new analytical quality control material ensuring comparability of chlorinated hydrocarbon analysis during an international environmental study in China.

A sediment reference material (S-37) was prepared as analytical quality control material to be used within an international project on polychlorinated hydrocarbon analysis in two Chinese rivers. The raw material was sampled during a cruise on Yangtse River and transported afterwards to the JRC Ispra for further processing. The material was treated according to the general principles applicable for candidate reference material production. After a thorough homogeneity study of the bulk the material was bottled. A total of 1,080 bottles each containing 50 g of dry sediment powder was obtained. Final homogeneity and stability testing proved the material to be fit for the purpose. Isotope dilution GC/MS was used to establish target values for pentachlorobenzene (1.17 +/- 0.08 ng/g), hexachlorobenzene (3.60 +/- 0.17 ng/g), octachlorostyrene (0.19 +/- 0.01 ng/g), pentachloroanisole (0.52 +/- 0.02 ng/g), alpha-HCH (0.70 +/- 0.05 ng/g), beta-HCH (1.38 +/- 0.18 ng/g), gamma-HCH (0.83 +/- 038 ng/g), 2,4'-DDT (0.36 +/- 0.04 ng/g), 2,4'-DDE (0.29 +/- 0.02 ng/g), 2,4'-DDD (0.49 +/- 0.02), 4,4'-DDT (3.42 +/- 0.47 ng/g), 4,4'-DDD (1.29 +/- 0.17 ng/g), PCB 28 (0.11 +/- 0.01 ng/g), PCB 52 (0.09 +/- 0.003 ng/g), PCB 101 (0.07 +/- 0.003 ng/g), PCB 138 (0.06 +/- 0.003 ng/g) and PCB 153 (0.06 +/- 0.003 ng/g). Furthermore, indicative values for major and minor constituents as well as for polychlorinated dibenzodioxines and -furanes were measured.

China↗
PubMed2000

On the presence of PCDD/Fs and other chlorinated hydrocarbons in the second generation of the European Reference Soil Set--the EUROSOILS.

The second generation of the European Reference Soil-Set, the so-called EUROSOILS, has been introduced recently. The presence of organic micro-pollutants in this new type of reference materials has already been studied for polycyclic aromatic hydrocarbons, triazines, phenylureas and other pesticides. The already large amount of data concerning the level of different contaminants, the elemental composition and matrix properties is completed by a survey by means of GC/MS on the polychlorinated dibenzodioxins/furans (PCDD/Fs) and other chlorinated hydrocarbons. Higher concentrations for 4,4'-DDT in EUROSOIL 2 (10.57 +/- 0.02 ng/g), for dieldrin in EUROSOIL 3 (8.85 +/- 0.87 ng/g) and for heptachlor-epoxide in EUROSOIL 4 (5.86 +/- 0.16 ng/g) could be detected. Sum concentrations for PCDD/Fs were 15.02 ng/kg (EUROSOIL 1), 214.29 ng/kg (EUROSOIL 2), 873.32 ng/kg (EUROSOIL 3), 54.47 ng/kg (EUROSOIL 4) and 119.61 ng/kg (EUROSOIL 5).

Benzofurans↗
PubMed2000

A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs).

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted.

Benzofurans↗
PubMed2000

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene.

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C2 through C8 organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.

Acetylene↗