Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Assessment of aluminum bioavailability in alum sludge for agricultural utilization

Inorganic aluminum ions, [Al(H₂O)₆]³⁺, [Al(OH)(H₂O)₅]²⁺, and [Al(OH)₂(H₂O)₄]⁺, are toxic to a number of crops. The aim of this study was to estimate the danger of soil contamination of bioavailable aluminum and heavy metals forms because of alum sludge which was a by-product of water, and wastewater treatment technology using aluminum coagulant is introduced into the soil. Aluminum and selected heavy metal fractionation was carried out in the post-coagulation sludge collected at a water treatment plant (where aluminum was used as a coagulant), fermented sewage sludge at a municipal wastewater treatment plant (which did not apply aluminum coagulant), and soil from water treatment plant as well as the mixtures of sludge and soil. It has been found that post-coagulation sludge used as natural fertilizer is a secondary source of bioavailable aluminum, especially when aluminum coagulants are used during water and wastewater treatment. The evaluation of applicability of the sludge to very weak acidic and acidic agricultural soils was carried out. The authors shall debate the question whether, in this case, the Regulation of EU and Polish Government on sewage sludge should also take the bioavailable aluminum into account and add to the list of the elements whose allowable contents are limited.     

Biomonitoring of heavy metals (Cd,Hg, and Pb) and metalloid (As) with the Portuguese common buzzard (Buteo buteo)

The accumulation of heavy metals in the environment may have a wide range of health effects on animals and humans. Thus, in this study, the concentrations of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in the blood and tissues (liver and kidney) of Portuguese common buzzards (Buteo buteo) were determined by inductively coupled plasma-mass spectrometer (ICP-MS) in order to monitor environmental pollution to these elements. In general, Hg and As were the elements which appeared in the highest and lowest concentrations, respectively. A highest percentage of non-detected concentration was found for blood Cd (94.6 %) but, in turn, it was the only metal that was detected in all kidney samples. The kidney was the analyzed sample which showed the highest concentrations of each element evaluated. Statistically, significant differences among blood, liver, and kidney samples were observed for As and Cd (P?相似文献   

Chthamalus montagui as biomonitor of metal contamination in the northwest coast of Portugal

The concentrations of seven metals (Cd, Cr, Cu, Fe, Mn, Ni and Zn) were determined in coastal seawaters and soft and hard tissues of the barnacle Chthamalus montagui from the northwest coast of Portugal to assess the potential use of C. montagui as biomonitor of metal contamination. The results of this study showed that C. montagui soft tissues can be used for monitoring metal bioavailabilities in these coastal seawaters: (1) there were significant correlations (p?相似文献   

Environmental and biological monitoring of benzene in traffic policemen, police drivers and rural outdoor male workers

To evaluate exposure to benzene in urban and rural areas, an investigation into personal exposure to benzene in traffic policemen, police drivers and rural (roadmen) male outdoor workers was carried out. Personal samples and data acquired using fixed monitoring stations located in different areas of the city were used to measure personal exposure to benzene in 62 non-smoker traffic policemen, 22 police drivers and 57 roadmen. Blood benzene, urinary trans-trans muconic acid (t,t-MA) and S-phenyl-mercapturic acid (S-PMA) were measured at the end of work shift in 62 non-smoker traffic policemen, 22 police drivers and 57 roadmen and 34 smoker traffic policemen, 21 police drivers and 53 roadmen. Exposure to benzene was similar among non-smoker traffic policemen and police drivers and higher among non-smoker urban workers compared to rural workers. Blood benzene, t,t-MA and S-PMA were similar among non-smoker traffic policemen and police drivers; blood benzene and t,t-MA were significantly higher in non-smoker urban workers compared to rural workers. Significant increases in t,t-MA were found in smokers vs. non-smokers. In non-smoker urban workers airborne benzene and blood benzene, and t,t-MA and S-PMA were significantly correlated. This study gives an evaluation of the exposure to benzene in an urban area, comparing people working in the street or in cars, to people working in a rural area. Benzene is a certain carcinogen for humans. The results we showed should lead to more in-depth studies about the effects on health of these categories of workers.     

Goose barnacle Pollicipes pollicipes as biomonitor of metal contamination in the northwest coast of Portugal

The main objective of this work was to assess the potential use of goose barnacle Pollicipes pollicipes as biomonitor of metal contamination in northwest (NW) coast of Portugal. The concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn were determined in coastal seawaters and tissues of P. pollicipes, which allowed establishing correlations between metals in coastal seawaters and P. pollicipes and calculating metal bioaccumulation factors (BAFs). The results of this study showed that P. pollicipes soft tissues can be used for monitoring metal contamination in these coastal seawaters: (1) there were significant correlations (p??0.05); (2) soft tissues were sensitive to spatial variations of metal bioavailabilities and their concentrations ranged 0.70-2.22?mg?Cd?kg(-1), 0.49-1.40?mg?Cr?kg(-1), 1.37-2.07?mg?Ni?kg(-1), 2.4-3.3?mg?Cu?kg(-1), 5-59?mg?Mn?kg(-1), 134-578?mg?Fe?kg(-1)and 728-1,854?mg?Zn?kg(-1); (3) mean logarithmic bioaccumulation factors (log BAF) of Fe, Cd and Zn were higher, 5.57, 5.47 and 4.41, respectively, than mean log BAFs of Cr, Mn, Cu and Ni, 4.18, 4.14, 3.98 and 3.51, respectively. In contrary, P. pollicipes shell plates were not considered ideal material to monitor metal bioavailabilities in these coastal seawaters. Regarding the very high concentrations of Zn obtained in the coastal seawaters and P. pollicipes soft tissues, the NW coast of Portugal should be classified as "Class III/IV - Remarkably/Highly Polluted".