Background, Aims and Scope Releasing agents, applied in the aluminium diecasting process, usually consist of water, oils, waxes, polysiloxanes, as well
as of a set of additives like emulsifiers, corrosion inhibitors, and biocides. During spray application and part release,
gases and aerosols are emitted into workplace air. The chemical compositions of these emissions are determined by the components
of the releasing agents and their reaction products formed during thermal stress of more than 700 °C. In the frame of the
joint project, the analytical tasks were to develop an appropriate sampling strategy for this production environment, to draw
conclusions about the occurrence of hazardous chemicals from production plant studies and from laboratory-scale thermolysis
experiments, and to determine the biodegradability of customary releasing agents.
Methods During realistic test production, active air sampling was performed in a production hall using different adsorption materials.
Cotton fabric sheets were positioned in the production area as passive samplers. Thermolysis experiments were performed at
600 °C with sealed quartz ampoules. The biodegradability of different releasing agents was determined according to German
industry standard DIN 51828 (2000). For analyses, GC/MS (headspace), FTIR, HPLC, IC, and ICP-OES techniques were applied.
Results and Discussion The substance spectrum, which was found in workplace air, was dominated by saturated and non-saturated aliphatic hydrocarbons.
Besides these, alcohols, alkyl phenols, xylenes and other benzene derivatives, aldehydes, glycols, carboxylic acid esters,
and amides were present. The German limiting value of 40 mg/m3 of complex hydrocarbon mixtures in a diecasting workplace atmosphere
was clearly under-run. Total hydrocarbon contents ranged between 2.7 and 6.3 mg/m3. Five different PAH were found in the air
close to the diecasting machine, with maximum concentrations between 0.05 and 3.06 μg/m3. Concentrations of nonylphenols ranged
from 10 to 200 μg/m3, and those of triethanolamine from 20 to 30 μg/m3. From 17 elements analyzed, only B, Fe, P, S, Si, and
Ti were emitted in small amounts. It was striking that the PAH patterns resulting from thermolysis experiments were quite
the same compared to those determined during the diecasting process. An influence of water and of Fe/Al on the composition
of the thermolysis products could mostly be shown. The degrees of biodegradation of three releasing agent extracts after 21
days were 21%, 29%, and 55%, respectively.
Conclusion A sampling strategy was developed, which allows an emission assessment for the industrial process of aluminium diecasting.
It enabled one to control limiting values, to characterise a wide variety of compounds emitted, and to identify and quantify
relevant pollutants. Only a few hazardous substances could be detected during the exemplary use of one releasing agent within
the compounds emitted into workplace air. Indications were found, that the prediction of the formation of harmful substances
from releasing agent components should be possible via thermolysis experiments. The biodegradability test can serve to assess
the expenditure of disposal of the usual leakage run-off of excess agent during production.
Recommendation and Outlook Investigations on further differently composed releasing agents, e.g. powders, would be desirable. A substitution of nonylphenol
ethoxylates by less harmful components would surely be an improvement of a releasing agent with regard to work safety and
health care, because of avoiding the emission of toxic and endocrine active nonylphenols. The surprisingly wide range of biodegradability
of the investigated releasing agents points to an optimization potential, that has obviously not yet been considered. 相似文献
Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the MicrotoxTM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).
Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.
Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water. 相似文献
Background, Aims and Scope In oil spill investigations, one of the most important steps is a proper choice of approaches that imply an investigation
of samples taken from different sedimentary environments, samples of oil contaminants taken in different periods of time and
samples taken at different distances from the oil spill. In all these cases, conclusion on the influence of the environment,
microorganisms or migration on the oil contaminants' composition can be drawn from the comparison of chemical compositions
of the investigated contaminants. However, in case of water contaminants, it is very important to define which part of organic
matter has been analyzed. Namely, previous investigations showed that there were some differences in chemical composition
of the same oil contaminant depending on the intensity of its contact with ground water. The aim of this work is to define
more precisely the interactions between oil contaminant and water, i.e. the influence of the intensity of interaction between
the oil contaminant and water on its chemical composition. The study was based on a comparison of four fractionated extracts
of an oil pollutant, after they had been analyzed in details.
Methods Oil polluted surface water (wastewater canal, Pančevo, Serbia) was investigated. The study was based on a comparison of four
extracts of an oil contaminant: extract 1 (decanted part), and extracts 2, 3 and 4 (extracted by shaking for 1 minute, 5 minutes
and 24 hours, respectively). The fractionated extracts were saponified with a solution of KOH in methanol, and neutralized
with 10% hydrochloric acid. The products were dissolved in a mixture of dichloromethane and hexane, and individually fractionated
by column chromatography on alumina and silica gel (saturated hydrocarbon, aromatic, alcohol and fatty acid fractions). n-Alkanes
and isoprenoid aliphatic alkanes, polycyclic alkanes of sterane and triterpane types, alcohols and fatty acids were analyzed
using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). δ13CPDB values of individual n-alkanes in
the aliphatic fractions were determined using gas chromatography-isotope ratio monitoring-mass spectrometry (GC-irmMS).
Results and discussion. Extracts 1 and 2 are characterized by uniform distribution of n-alkanes, whereas extract 3 is characterized
by an even-numbered members dominating the odd-ones, and extract 4 showed a bimodal distribution. Extract 1 is characterized
by the least negative δ13CPDB values of C19-C26 n-alkanes. Sterane and triterpane analysis confirmed that all extracts originated
from the same oil contaminant. n-Fatty acids, C19-C24, in all extracts are very low, being somewhat higher in extract 4. Even-numbered
n-alcohols, C12–C16, were identified in the highest concentration in extract 3. It was assumed that algae were responsible
for the composition of extract 3. Furthermore, a possible reason for higher concentrations of C19–C26 n-alkanes and C19–C24
fatty acids in extract 4 is the formation of inclusion compounds with colloidal micelles formed between the oil contaminant's
NSO-compounds and water.
Conclusion It was undoubtedly confirmed that there were specific differences in the compositions of the different extracts depending
on the intensity of the interaction between the oil contaminant and the surface water.
Recommendation and Outlook. When comparing the composition of oil contaminants from different water samples (regardless of
the ultimate investigation goal) it is necessary to compare the extracts isolated under the same conditions, in other words,
extracts that were in the same or very similar interaction with water. 相似文献
Humans show intra- and intersexual variation in second (2D) relative to fourth (4D) finger length, men having smaller 2D:4D ratio, possibly because of differential exposure to sex hormones during fetal life. The relations between 2D:4D and phenotypic traits including fitness components reported by several studies may originate from the organizational effects that sex hormones have on diverse organs and their concomitant effect on 2D:4D. Evolutionary theory posits that sexual preferences are adaptations whereby choosy individuals obtain direct or genetic indirect benefits by choosing a particular mate. Since sex hormones influence both fitness and 2D:4D, hand sexual attractiveness should depend on 2D:4D, a hypothesis tested only in one correlational study so far. We first presented hand computer images to undergraduates and found that opposite-sex hands with long 2D and 4D were considered more sexually attractive. When we experimentally manipulated hand images by increasing or decreasing 2D and/or 4D length, women preferred opposite-sex hands that had been masculinized by elongating 4D, whereas men avoided masculinized opposite-sex right hands with shortened 2D. Hence, consensus exists about which hands are attractive among different opposite-sex judges. Finger length may signal desirable sex hormone-dependent traits or genetic quality of potential mates. Psychological mechanisms mediating hand attractiveness judgments may thus reflect adaptations functioning to provide direct or indirect benefits to choosy individuals. Because the genetic mechanisms that link digit development to sex hormones may be mediated by Hox genes which are conserved in vertebrates, present results have broad implications for sexual selection studies also in nonhuman taxa. 相似文献
Objective: We conducted a cohort study of recent wartime veterans to determine the postservice mortality risk due to motor vehicle accidents (MVAs).
Methods: Veterans were identified from the Defense Manpower Data Center records. Deployment to te Iraq or Afghanistan war zone was determined from the Contingency Tracking System. Vital status of 317,581 deployed and 964,493 nondeployed veterans was followed from their discharge dates between 2001 to 2007 until earlier of date of death or December 31, 2009. Underlying causes of death were obtained from the National Death Index Plus.
Results: Based on 9,353 deaths (deployed, 1,650; nondeployed, 7,703), of which 779 were MVA deaths as drivers (166; 613), both cohorts had 25 to 24% lower mortality risk from all causes but had 44 to 45% higher risk of MVA deaths relative to the U.S. general population. The higher MVA mortality risk was not associated with deployment to the war zone. After controlling for age, sex, race, marital status, branch of service, and rank, the risk for deployed veterans was comparable to that of nondeployed veterans (hazard ratio = 0.91; 95% confidence interval, 0.77–1.09).
Conclusions: Veterans exhibit significantly higher risk of MVA deaths compared to the U.S. general population. However, deployment to the Iraq or Afghanistan war was not associated with the excess risk. 相似文献
Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 μg/kg on dry mass and the average contents in all of the 28 examined samples was 300 μg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7–48 μg/kg), anthracene (1–31 μg/kg), pyrene (1–970 μg/kg), benzo(a)anthracene (1–18 μg/kg) chrysene (17–365 μg/kg), benzo(a)pyrene (1–29 μg/kg), and indeno(1,2,3-cd)pyrene (4–119 μg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6). 相似文献
We exposed flour beetles (Tribolium castaneum) to a mixture of four poly aromatic hydrocarbons (PAHs). The experimental setup was chosen such that the emphasis was on assessing partial effects. We interpreted the effects of the mixture by a process-based model, with a threshold concentration for effects on survival. The behavior of the threshold concentration was one of the key features of this research. We showed that the threshold concentration is shared by toxicants with the same mode of action, which gives a mechanistic explanation for the observation that toxic effects in mixtures may occur in concentration ranges where the individual components do not show effects. Our approach gives reliable predictions of partial effects on survival and allows for a reduction of experimental effort in assessing effects of mixtures, extrapolations to other mixtures, other points in time, or in a wider perspective to other organisms. 相似文献