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Treatment of a foul condensate from Kraft pulping with horseradish peroxidase and hydrogen peroxide.

Foul condensates originating from the Kraft recovery process contain phenolic compounds whose removal might render these process streams more useful for reuse in other plant operations or more amenable to biological degradation. Treatment of a foul condensate with horseradish peroxidase and H2O2 selectively targeted phenolic compounds resulting in a reduction of the total phenols concentration below 1 mg/L as well as a substantial toxicity drop as measured using the Microtox assay; however, only marginal COD removal was achieved. Comparisons of treatments between synthetic wastewaters and real wastewaters to which phenol were added revealed that the condensate contained species that protect the enzyme from inactivation by reaction products. Analytical data as well as experimental results suggest that these species are lignin derivatives.

Benzothiazoles↗

Photocatalytic degradation of propachlor in aqueous TiO2 suspensions. Determination of the reaction pathway and identification of intermediate products by various analytical methods.

The light-induced degradation of propachlor (2-chloro-N-isopropylacetanilide) under simulated solar irradiation has been investigated in aqueous solutions containing TiO2 suspensions as photocatalysts. The study focuses on the identification of possible intermediate products and the determination of inorganic ions formed during the process, using several powerful analytical techniques such as gas chromatography mass-spectrometry (GC-MS) and ion chromatography. The primary degradation of propachlor has been a fast process with a half-live time of 2.3 min and followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. The mineralization of the organic carbon to CO2 after 240 min of irradiation was found to be < 63%. The corresponding stoichiometric transformation of organic chlorine into chloride ion was reached in 30 min, whereas oxidation of nitrogen to nitrate ions took place at delayed irradiation times. Various aromatic intermediates have been identified by GC/MS techniques during the treatment, which were involved into three tentative degradation routes. One, was based on the dechlorination through positive holes or solvated electrons to form the hydroxy or aliphatic derivative. The second route consists of the rupture of amide bond or the N-C bond via nitrogen ionization by positive holes and through the ring hydroxylation, respectively. Finally, the third possible degradation route was based on hydrogen abstraction by the hydroxyl radicals or positive holes, followed either by the addition of oxygen to the alkyl radical or the decomposition of the peroxyl radical formed. From the analytical data, a possible multi-step degradation scheme was proposed. This work points to the necessity of extended knowledge of the successive steps in a solar-assisted detoxification process.

Acetanilides↗

Toxicity of waters from two streams to early life stages of brown trout (Salmo trutta f. fario L.), tested under semi-field conditions.

The development of brown trout (Salmo trutta f. fario L.) in water of two differently polluted streams and in a control situation was monitored in order to get insights into the impact of anthropogenic chemical stressors on the reproductive success of this fish species indigenous to both streams. The test streams, situated in the south of Stuttgart, Germany, were the complexly polluted Körsch stream and the less polluted Krähenbach stream. Bypass systems connected to the streams and a laboratory control system were used for continuous exposure of early brown trout stages shortly after fertilisation up to the end of the embryonic development. Temperature and oxygen conditions were standardised in all test series in order to minimise unspecific effects. The examined endpoints were: (1) mortality, (2) developmental rate, (3) time course of hatching, (4) malformations, and (5) growth. A retarded development, reduced growth rates and higher mortality rates of Körsch stream water exposed embryos indicated an embryotoxic potential for the more polluted stream. High infection-related mortality rates of embryos suggested the presence of confounding factors also in the less polluted Krähenbach stream. In parallel to the exposure experiment, physicochemical and limnochemical parameters as well as concentrations of organic contaminants and heavy metals were monitored. Analytical data confirm the different degrees of pollution of both streams.

Animals↗

Formation of dioxin analogs by open-air incineration of waste wood and by fire of buildings and houses concerning Hanshin Great Earthquake in Japan.

Ash samples were collected from site of open-air incineration and fire concerning Hanshin Great Earthquake which occurred in western Japan in the early morning of 17 January 1995. The average concentrations of total sum of PCDDs, PCDFs and Co-PCBs in ash collected from wood scrap of broken building fire site, house fire site, shoe-making factory fire site and electric appliances store fire site were 541, 442, 859 and 22,800 pgTEQ/g, respectively. Particularly, PCDFs among dioxin analogs generated remarkably at sites with a high TEQ. In addition, 79,000 t of ash was totally produced at five open-air incineration sites, and consequently the formation amount of PCDDs, PCDFs and Co-PCBs was estimated to be 70.7 gTEQ on the basis of these analytical data.

Air↗

Literature survey of on-line spectroscopic methods for lead determination in environmental solid samples.

A review is presented where are shown the advantages involved in the use of flow injection (FI) analysis for the determination of lead in environmental solid samples by spectroscopic detectors. The FI methods proposed for the determination of lead in these samples are described and compared according to the detection technique used. Analytical data of interest and interferences are discussed for each technique.

Environmental Monitoring↗

Non-polar halogenated natural products bioaccumulated in marine samples. I. 2,3,3',4,4',5,5'-Heptachloro-1'-methyl-1,2'-bipyrrole (Q1).

This presentation adds new spectroscopic and analytical data on the natural product Q1 that was recently identified by synthesis as 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole. Solid state magic angle spinning 13C NMR data of Q1 is presented as an option for structural proof. Furthermore, the UV spectrum of neat Q1 (absorption maximum at 223 nm) was recorded and, with NMR spectroscopic data, confirmed a twisted bipyrrole ring system. A quantitative standard of Q1 was prepared which allowed to correct previous concentration estimates relative to the electron capture detector response factor of trans-nonachlor. As a result, the actual Q1 response was only 0.65+/-15% of the response factor of trans-nonachlor. Therefore, actual Q1 levels are about 50% higher than the previous estimates. With this result the highest (corrected) Q1 concentration determined to date in the blubber of marine mammals from Australia is 14 mg/kg lipid. Analysis of Q1 and trans-nonachlor in specimens from the German North Sea coast suggests that harbor seals are more able to metabolize Q1 than harbor porpoises. Finally, we calculated that 79 congeners of Q1 (i.e. lower chlorinated 1(')-methyl-1,2(')-bipyrroles) are theoretically possible and present their structures.

Animals↗

Eel-pout (Zoarces viviparus L.) as a marine bioindicator.

Several elements and metal species were analyzed in eel-pout or viviparous blenny (Zoarces viviparus). The analytical data demonstrate that fish muscle is a suitable bioindicator for mercury (Hg) and arsenic (As). About 90% of the total Hg content is present in the fish muscle in the form of methyl mercury. Due to higher concentration levels, the liver is more useful for monitoring Pb and TI. No biomagnification of some trace elements, such as Cd, Ni or Co, were observed in eel-pout. More information is necessary to decide about the use of eel-pout for long-time monitoring programs.

Aging↗

Non-ortho PCB levels in various fish species from the east and west coast of Sweden.

Non-ortho (coplanar) PCBs 77, 126 and 169 were determined in a number of fish species from the Swedish coastal environment, using either supercritical fluid extraction (SFE) or the traditional liquid/liquid extraction followed by HPLC separation on porous graphitic carbon (PGC) column prior to GC/MS analysis. While PCB 77 showed the highest concentration level, the TEQ value for PCB 126 was dominant in virtually all the samples analysed. The toxic equivalents, however, indicated some differences in analytical data between 1990 and 1992/93 but these are not significant probably owing to the short period in between.

Animals↗

Biogenic volatile organic compound emissions (BVOCs). II. Landscape flux potentials from three continental sites in the U.S.

Landscape flux potentials for biogenic volatile organic compounds (BVOCs) were derived for three ecosystems in the continental U.S. (Fernbank Forest, Atlanta, GA; Willow Creek, Rhinelander, WI; Temple Ridge, CO). Analytical data from branch enclosure measurements were combined with ecological survey data for plant species composition and biomass. Other quantitative flux measurements at the leaf and landscape level were incorporated to scale the results from the enclosure measurements to the landscape level. Flux estimates were derived by using a one week ambient temperature and light record (30 min time resolution) and adjusting all emission rates to these conditions with temperature and light correction algorithms.

Colorado↗

Distribution of lanthanoids, Be, Bi, Ga, Te, Tl, Th and U on the territory of Bulgaria using Populus nigra 'Italica' as an indicator.

The concentrations of lanthanoids, Be, Bi,Ga, Te, Tl, Th and U have been determined using ICP-MS for 100 standardized samples of poplar leaves collected from the territory of Bulgaria. The investigated elements are log-normally distributed on the territory. Using cluster analysis of the analytical data the samples were grouped according soil type on which the plants are growing.

Bulgaria↗

Trace element levels in whole blood samples from residents of the city Badajoz, Spain.

Copper, lead, cadmium, and zinc were determined by anodic stripping voltammetry after sample digestion and potentiometric stripping analysis was used for Pb and Cd determination in original samples. Selenium was determined by cathodic stripping voltammetry or hydride generation AAS. Element levels found in the whole blood sample in a group of 82 people are for Cd: 0.98 +/- 0.94 ng/ml; for Pb: 46.7 +/- 28.6 ng/ml; for Cu: 1.07 +/- 0.12 micrograms/ml; for Zn: 6.95 +/- 1.08 micrograms/ml, and for Se: 116 +/- 25 ng/ml. Analytical data have been correlated to age, sex, smokers or non-smokers, drinking and food habits.

Adult↗

Screening of heavy metal pollution in Bulgaria using Populus nigra 'Italica'.

The pollution with As, Cd, Co, Cr, Cu, Fe, Mn, Pb, Sb and Zn on the territory of Bulgaria has been evaluated using standardized samples of leaves of Populus nigra 'Italica' collected during the last 10 years. Background values for the respective elements are established in the leaves of the plant. The comparisons of urban and industrial pollution to some other European countries indicates similar or lower concentrations. Using cluster analysis of the analytical data the territory of Bulgaria is divided into six regions with different pollution levels.

Air Pollutants↗

Investigation of the dissolution of the bioceramic hydroxyapatite in the presence of titanium ions using ToF-SIMS and XPS.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) analyses have been used to investigate the dissolution of hydroxyapatite in the presence of titanium chloride suggesting the substitution of titanium ions for calcium in the hydroxyapatite structure. The surface analytical data suggest that titanium was incorporated within the solid phase as titanium phosphate. Comparison of relative ion intensities in the ToF-SIMS spectra reveals changes in the composition of the surface chemistry of hydroxyapatite. These relative ion intensities show that the maximum surface uptake of titanium occurred at a solution concentration of 500 ppm titanium chloride for a time of incubation of 30 min. These data correlate with that obtained using XPS highlighting the semi-quantitative information which ToF-SIMS can provide.

Biocompatible Materials↗

Peripheral blood lymphocyte subset shifts in patients with untreated hematological tumors: evidence for systemic activation of the T cell compartment.

Flow cytometry immunophenotyping of peripheral blood lymphocyte subsets and multivariate data-analytical techniques revealed that among untreated hemato-oncological patients (n = 48) with lymphomas, acute and chronic myeloid and lymphocytic leukemias, monoclonal gammopathy of undetermined significance, and multiple myeloma, 42% had (nonmalignant) lymphocyte profiles clearly distinct from healthy donors. Notably, a similar pattern of increased CD3+ CD57+, CD3+ HLA-DR+, CD3+ CD(16 + 56)+, CD4- CD8+, CD8+ CD57+, CD8+ CD28-, and CD8+ CD62L- subsets was detected. More extensive three-color immunophenotyping on an additional group of 49 untreated patients revealed that both CD4+ and CD8+ T cells displayed significant increases of activation markers: CD69, CD(16 + 56), HLA-DR, CD71, and CD57, and a loss of CD62L and CD28, which is also interpreted as a sign of activation. Consistent with the phenotypical signs of in vivo immune activation, polyclonal cytolytic activity, measured ex vivo in an anti-CD3-redirected assay, was detected within immunomagnetically purified CD4+ T cells of three out of six B-CLL patients investigated, but not within purified CD4+ T cells of five healthy donors. The purified CD8+ T cells of patients (n = 28) and donors (n = 5) on the other hand displayed similar polyclonal cytotoxic activities at the various effector:target ratios investigated. Tumor-directed cytotoxic activity of purified CD4+ (n = 6) and/or CD8+ T cells (n = 15) against freshly isolated autologous tumor cells was not detected in any of the experiments. Collectively, our results demonstrate systemic T cell activation as a common feature in hematological neoplasia, and a markedly enhanced cytolytic activity of the CD4- subset in CLL patients. The reason(s) for this expansion of activated T cells and its pathophysiologic significance, however, remain unclear.

Adolescent↗

Social correlates and coping measures of street-children: a comparative study of street and non-street children in south-western Nigeria.

OBJECTIVE: This paper sought to achieve two objectives: First, to identify the social correlates attributable to street-children in south-western Nigeria as well as predisposing factors to this behavior; second, it also tried to uncover the survival mechanisms of street children. METHOD: The study was carried out in Ibadan and Lagos metropoles in south-western Nigeria. A pilot study was first conducted to clarify issues like location of the children on the streets, time of the day suitable for interview, and adequacy of the instruments. The main study involving a comparative 202 and 201 street-children and non-street children, respectively, was carried out using the questionnaire and case study approach in the two cities. Data analytical procedures involved both quantitative and qualitative methods. RESULTS: Street-children are mostly males, have low-levels of education, are predominantly Yoruba, and come from families with five or more siblings. Parents of street-children commonly had low education and were mainly found in unskilled occupations: were in contract polygynous marriages which are also often characterized by marital disruption. Street children also left home because of parental/familial reasons, chiefly among which was the inability of their parents to meet with their expectations. They survive on the streets engaging in some income-yielding activities, and are also faced with many hazards. CONCLUSIONS: The findings revealed that polygyny, large family, family disruption, and child labor were all central issues and predisposing factors to living on the streets by children. The poverty factor clearly came out as a very important factor.

Adaptation, Psychological↗

Untreated abandoned mercury mining works in a scenic area of Asturias (Spain).

Mercury mining was a large and thriving industry during the last century in Asturias (NW Spain). At Brañalamosa, mining activity introduced significant quantities of wastes in spoil heaps located close to the mining operations. In these mining wastes, in addition to mercury, high concentrations of other potentially dangerous elements like As have been found. As a consequence, pollution and dereliction of the local environment occurred. This paper focuses on the environmental impact of these old mining operations and describes a preliminary assessment of the extent of contamination. This includes analytical data from systematic sampling of soils, stream sediments, wastes from spoil heaps, water and herbaceous plants in areas affected by mining activities. The potential risk that spoil materials imply for human health and the environment is documented on the basis of the application of EPA Risk Assessment methodology.

Arsenic↗

Reactivity of Cd7-metallothionein with Cu(II) ions: evidence for a cooperative formation of Cd3,Cu(I)5-metallothionein.

Reaction of Cd7-metallothionein-2 (MT) with Cu(II) ions has been studied by a variety of spectroscopic techniques including UV-absorption, circular dichroism (CD) and luminescence spectroscopy. The addition of up to 5 Cu(II) equivalents to Cd7-MT resulted in a cooperative formation of the monomeric Cd3,Cu5-MT form, as revealed by the analytical data and the presence of isosbestic or isodichroic points in the respective UV and CD spectra. The presence of Cu(I) luminescence and the absence of Cu(II) EPR signal indicated that copper is bound in the Cu(I) oxidation state, i.e., Cd3,Cu(I)5-MT. Consequently, the reduction of Cu(II) ions is accompanied by the oxidation of thiolate ligands of the protein. The absorption features and the luminescence data at 77 K are consistent with the presence of an air-stable Cu(I)-cluster in Cd3,Cu(I)5-MT. The participation of other ligands, besides cysteine thiolates, in metal coordination cannot be ruled out. With more than 5 Cu(II) equivalents added a mixture of unstable MT metalloforms were formed. The concomitant reduction and binding of copper ions by metallated MT represent a new aspect of the MT structure.

Cadmium↗

New methyl pyruvate thiosemicarbazones and their copper and zinc complexes: synthesis, characterization, X-ray structures and biological activity.

By reacting thiosemicarbazides substituted on the aminic nitrogen with both alkyl or aryl groups, and methyl pyruvate a new group of methylpyruvate thiosemicarbazones (Hmpt) derivatives was obtained. These ligands were then treated with copper and zinc inorganic salts. All isolated compounds were characterized using spectroscopic methods. The single crystal structural analysis of the ligands Me-Hmpt x 0.5H2O 1, Et-Hmpt x H2O 2, Ph-Hmpt 5, Meph-Hmpt 6 showed that only compound 6 presents significant deviation from planarity. The X-ray structure of [Zn(Me-Hmpt)Cl2] x H2O 8 showed that in this complex Me-Hmpt behaves as a neutral ligand SNO terdentate and that the penta coordination is achieved by chloride ions according to spectroscopic and elemental analyses. On the basis of the analytical data the same behavior is proposed for the other zinc complexes. All the ligands in copper complexes seem to be monodeprotonated; nevertheless the same SNO behavior is expected. Tests on cell proliferation of human leukemic cell line U937 showed that the copper complex Cu(Et-mpt)Cl x H2O is the most active compound among those reported even though it is not able to induce apoptosis.

Apoptosis↗