Formation and emission of chloroanisoles as indoor pollutants

GOAL, SCOPE AND BACKGROUND: Complaints by residents of frame-houses about musty odour in the houses has become an increasing problem within the last years. An additional problem is that the odour is transferred to clothes and skin. The persons themselves do not recognize the smell after a while because of adaptation. Serious social problems are the result. For a long time, the smell was explained to be from mould due to construction-based humidity problems. However, in an increasing number of houses, no indications were found for elevated levels of mould growth. METHODS: Air and material samples were taken from 5 houses, which show typical musty odours, and analysed with respect to chlorophenols and chloroanisoles. Additionally, some samples were analysed for lindane and its metabolites, because lindane was commonly used together with pentachlorophenol (PCP) for wood protection. RESULTS AND DISCUSSION: Meticulous analysis resulted in the identification of chloroanisoles, mainly 2,3,4,6-tetrachloroanisole. These substances are known from corky wines and from contamination of food from pentachlorophenol (PCP) treated pallets and result from microbiological metabolic processes. Pentachlorophenol was commonly used to protect wood from fungi in Germany mainly in the later 60s and 70s. Details of these processes, as well as effective methods to identify chloroanisoles in the problem houses, are described. CONCLUSIONS: Chloroanisoles formed by metabolism of PCP have been well known to contaminate food or wine. Here, they were identified and are probably responsible for the musty odours in the frame houses. Since it is quite clear that these substances were not components of building materials used in the houses, an explanation for chloroanisole formation is proposed. Localized dampness probably favours microbial growth associated with metabolic conversion of chlorophenols to the corresponding chloroanisoles, primarily 2,3,4,6-tetrachloroanisol, which spread throughout the buildings, resulting in the observed odours. RECOMMENDATIONS AND OUTLOOK: The group of chloroanisoles has been recognized as important indoor pollutants as they possess musty odours at extremely low concentrations, e.g. for 2,4,6-trichloroanisole in a range of 5-10 ppt in air (Staples 2000). On the basis of currently available toxicological data, exposure of the occupants to the concentrations of chloroanisoles measured is not associated with a health risk. No correlation could be observed between concentrations of chloroanisoles and PCP in house dust and indoor air. However, chloroanisoles are good indicators for possible PCP-treatment of wood in frame houses and their detection should initiate investigations on PCP contamination. Research is continuing to identify the microorganisms involved and to devise a remediation procedure for affected houses.     

The importance of glutathione and phytochelatins on the selenite and arsenate detoxification in Arabidopsis thaliana

We investigated the role of glutathione(GSH) and phytochelatins(PCs) on the detoxification of selenite using Arabidopsis thaliana. The wild-type(WT) of Arabidopsis thaliana and its mutants(glutathione deficient Cad 2–1 and phytochelatins deficient Cad 1–3) were separately exposed to varying concentrations of selenite and arsenate and jointly to both toxicants to determine their sensitivities. The results of the study revealed that, the mutants were about 20-fold more sensitive to arsenate than the WT, an indication that the GSH and PCs affect arsenate detoxification. On the contrary, the WT and both mutants showed a similar level of sensitivity to selenite, an indication that the GSH and PCs do not significantly affect selenite detoxification. However, the WT is about 8 times more sensitive to selenite than to arsenate, and the mutants were more resistant to selenite than arsenate by a factor of 2. This could not be explained by the accumulation of both elements in roots and shoots in exposure experiments. The co-exposure of the WT indicates a synergistic effect with regards to toxicity since selenite did not induce PCs but arsenic and selenium compete in their PC binding as revealed by speciation analysis of the root extracts using HPLC–ICP–MS/ESI–MS. In the absence of PCs an antagonistic effect has been detected which might suggest indirectly that the formation of Se glutathione complex prevent the formation of detrimental selenopeptides. This study, therefore, revealed that PC and GSH have only a subordinate role in the detoxification of selenite.     

Concentrations of microcystins in tissues of several fish species from freshwater reservoirs and ponds

The aim of this study is to summarise the determination of concentrations of microcystins (MCs) in muscle and liver of freshwater fish species caught in stagnant waters of the Czech Republic. Within the years 2007–2009, 351 muscle samples and 291 liver samples of 16 freshwater fish species derived from four fishponds, and four water reservoirs were analysed. MCs were detected in 53 liver samples. The highest concentrations of microcystins were determined in liver samples of carnivorous fish species; 50.3 ng/g of fresh weight (FW) in perch (Perca fluviatilis) and 22.7 ng/g FW in pikeperch (Sander lucioperca). MCs in liver were detected in other five fish species; asp (Aspius aspius), pike (Esox lucius), common carp (Cyprinus carpio), grass carp (Ctenopharyngodon idella) and European eel (Anguilla anguilla). Concentrations of MCs in liver of nine fish species (European bream, whitefish, tench, silver carp, European catfish, roach, chub, crucian carp and rudd) were below the detection limit of 1.2–5.4 ng/g FW for different MC congeners. However, the concentrations of MCs in all muscle samples were below the detection limit. The assessment of MCs concentrations might be influenced by the detection method used. Due to the concentrations of MCs being below the detection limit in muscle samples of all fish species analysed, it seems that there might be a low potential threat for human health in case of fish muscle consumption.     

Full-scale use of glycogen-accumulating organisms for excess biological carbon removal

The purpose of this study has been to verify the efficient full-scale applicability of glycogen-accumulating organisms (GAOs) for excess biological carbon removal, that is, for removing more carbon substrate than the amount of available nutrients would allow in the conventional activated sludge process of microbial growth. This aims to cost-effectively overcome the problem of viscous bulking occurring in a fully aerated system, with nutrient deficiency. Analytical data measured at the wastewater treatment plant of the Balatonboglár (BB) winery in Balatonboglár, Hungary, containing consecutive unaerated and aerated activated sludge basins, reflected a high performance with efficient carbon removal and good sludge settling, without dosing any external nutrient source to the severely nitrogen- and phosphorous-deficient influent. Supplementary laboratory-scale batch experiments and microbiological tests verified the abundance of GAOs in the activated sludge system and elucidated their role in efficient excess biological carbon removal.     

Food alert patterns for metal contamination analyses in seafoods: Longitudinal and geographical perspectives

The aims of this study are to explore metal contamination in food with respect to variations in: i) the levels found over a period of eleven months and/or ii) by food types; and iii) to report patterns in reporting between countries. The frequencies of reported cases of metal ion contamination were ≤ 25% of total food alerts with notable increases between June and October. The alerted food products were dominated by seafood, where the majority were due to Mercury contamination and were made by EU member states with Italy making 57 of the 102 reports. The contaminated seafoods originate in thirty two countries with only Spain producing over 10 contaminated seafood products with a total of 47. In conclusion, this analysis highlights the main detector and transgressor nations along with the seafood and metal types that lead to alerts owing to high levels of contamination.     

Urinary methyl tert-butyl ether and benzene as biomarkers of exposure to urban traffic

Methyl tert-butyl ether (MTBE) and benzene are added to gasoline to improve the combustion process and are found in the urban environment as a consequence of vehicular traffic. Herein we evaluate urinary MTBE (MTBE-U) and benzene (BEN-U) as biomarkers of exposure to urban traffic. Milan urban policemen (130 total) were investigated in May, July, October, and December for a total of 171 work shifts. Personal exposure to airborne benzene and carbon monoxide (CO), and atmospheric data, were measured during the work shift, while personal characteristics were collected by a questionnaire. A time/activity diary was completed by each subject during the work shift. Spot urine samples were obtained for the determination of MTBE-U and BEN-U. Median personal exposure to CO and airborne benzene were 3.3 mg/m(3) and 9.6 μg/m(3), respectively; median urinary levels in end-of-shift (ES) samples were 147 ng/L (MTBE-U) and 207 ng/L (BEN-U). The time spent on traffic duty at crossing was about 40% of work time. Multiple linear regression models, taking into account within-subject correlations, were applied to investigate the role of urban pollution, atmospheric conditions, job variables and personal characteristics on the level of biomarkers. MTBE-U was influenced by the month of sampling and positively correlated to the time spent in traffic guarding, CO exposure and atmospheric pressure, while negatively correlated to wind speed (R(2) for total model 0.63, P<0.001). BEN-U was influenced by the month and smoking habit, and positively correlated to urinary creatinine; moreover, an interaction between CO and smoking was found (R(2)=0.62, P<0.001). These results suggest that MTBE-U is a reliable marker for assessing urban traffic exposure, while BEN-U is determined mainly by personal characteristics.     

Acute and sub-chronic toxicity of four cytostatic drugs in zebrafish

The acute and sub-chronic effects of four cytostatic drugs—5-fluorouracil (5-FU), cisplatin (CisPt), etoposide (ET) and imatinib mesylate (IM)—on zebrafish (Danio rerio) were investigated. Acute tests were carried out in a static system in accordance with the OECD guideline 203 for adult fish and the draft guideline for fish embryos (FET test) in order to find the LC50 values of the four cytostatic drugs. Early-life stage toxicity test on zebrafish was conducted according the OECD guideline 210 using the cytostatic drugs 5-FU and IM in a semistatic system with the objective of investigating the sub-chronic effects of the cytostatic drugs on fish. In adult fish, the cytostatic drugs 5-FU and ET did not pass the limit test, thus, are considered non-toxic. In case of cisplatin, LC50 was calculated at 64.5 mg L^?1, whereas in case of IM, LC50 was at 70.8 mg L^?1. In the FET test, LC50 of 5-FU at 72-h post fertilization (hpf) was 2441.6 mg L^?1. In case of CisPt, LC50 was 349.9 mg L^?1 at 48 hpf and it progressively decreased to 81.3 mg L^?1 at 120 hpf. In addition, CisPt caused a significant delay in the hatch of larvae. In case of ET, LC50 values were not calculable as they were higher than 300 mg L^?1 at which concentration the substance crystallized in the solution. LC50 values of IM were 48 hpf; 158.3 mg L^?1 , 72 hpf; 141.6 mg L^?1, 96 hpf; 118.0 mg L^?1, and 120 hpf; 65.9 mg L^?1. In the Early-life Stage Test with 5-FU, embryonic deformities were not detected during the tests. Regarding mortalities, the 10 mg L^?1 concentration can be considered as LOEC, as statistically significant difference in mortalities was detected in this group alone. Concerning dry body weight and standard length, 1 mg L^?1 is the LOEC. In case of IM, the highest tested concentration (10 mg L^?1) can be considered LOEC for mortalities, however, the treatment did not have an effect on the other investigated parameters (dry and wet weight, standard length). All four cytostatic drugs were characterized by low toxicity in zebrafish in acute and sub-chronic tests.     

<Emphasis Type="Italic">Ailanthus Altissima</Emphasis> and <Emphasis Type="Italic">Phragmites Australis</Emphasis> for chromium removal from a contaminated soil

The comparative effectiveness for hexavalent chromium removal from irrigation water, using two selected plant species (Phragmites australis and Ailanthus altissima) planted in soil contaminated with hexavalent chromium, has been studied in the present work. Total chromium removal from water was ranging from 55 % (Phragmites) to 61 % (Ailanthus). After 360 days, the contaminated soil dropped from 70 (initial) to 36 and 41 mg Cr/kg (dry soil), for Phragmites and Ailanthus, respectively. Phragmites accumulated the highest amount of chromium in the roots (1910 mg Cr/kg_{(dry tissue)}), compared with 358 mg Cr/kg_{(dry tissue)} for Ailanthus roots. Most of chromium was found in trivalent form in all plant tissues. Ailanthus had the lowest affinity for Cr^VI reduction in the root tissues. Phragmites indicated the highest chromium translocation potential, from roots to stems. Both plant species showed good potentialities to be used in phytoremediation installations for chromium removal.     

Sunlight-induced degradation of soil-adsorbed veterinary antimicrobials Marbofloxacin and Enrofloxacin

Marbofloxacin (MAR) and Enrofloxacin (ENR), two largely employed veterinary Fluoroquinolones (FQs), were found to be present at the micrograms per kilogram level in agricultural soils of South Lombardy (Italy) several months after manuring. Distribution coefficients (K_d) from sorption experiments indicated a strong binding to the soil. Soil samples fortified with environmentally significant FQs amounts (0.5 mg kg⁻¹) were exposed to solar light that promoted extensive degradation (80%) of both drugs in 60-150 h. Thus, photochemistry could be considered a significant depollution path in the soil, although it was two orders of magnitudes slower than in aqueous solution and a fraction of the drug (ca. 20%) remained unaffected. For MAR the photoprocess was the same as in solution, and involved cleavage of the tetrahydrooxadiazine ring. On the contrary, with ENR only some of the photoproducts determined in water (those arising from a stepwise oxidation of the piperazine side chain) were observed. Substitution of the 6-fluoro by a hydroxyl group and reduction did not occur in the soil, supporting the previous contention that such processes required polar solvation of FQs. Consistently with this rationalization, the irradiation of thin layers of solid drugs led to essentially the same products distribution as in the soil. From the environmental point of view it is important to notice that photodegradation mainly affects the side-chains, while the fluoroquinolone ring, to which the biological effect is associated, is conserved up to the later stages of the degradation.