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Determination of natural and synthetic glucocorticoids in effluent of sewage treatment plants using ultrahigh performance liquid chromatography-tandem mass spectrometry Full text
2015
Isobe, Tomohiko | Sato, Kentaro | Joon-Woo, Kim | Tanabe, Shinsuke | Suzuki, Go | Nakayama, Kei
A sensitive and comprehensive analytical method for glucocorticoids (GCs) in water samples was developed and applied to effluent of sewage treatment plants (STPs). In the present study, totally 10 natural and synthetic GCs, including cortisol, betamethasone valerate, clobetasol propionate, clobetasone butyrate, difluprednate, betamethasone, dexamethasone, betamethasone dipropionate, methylprednisolone, and prednisolone, were targeted. Analytes were extracted and concentrated using an OASIS HLB solid phase extraction cartridge. Chromatographic separation and quantification were achieved using an ultrahigh performance liquid chromatograph coupled with a tandem mass spectrometer (UHPLC-MS/MS). Method detection limits were 0.05 to 0.89 ng/L, which were 1–2 orders of magnitude more sensitive than in the previous reports. Cortisol was detected in more than half of (27 out of 50) analyzed effluent samples at concentrations in the range of ND-1.36 ng/L, indicating continuous discharge of natural GC via STP effluent. On the other hand, dexamethasone + betamethasone, prednisolone, betamethasone valerate, and clobetasol propionate were detected in 25, 8, 20, and 9 samples among 50 effluent samples, respectively, suggesting not extreme but significant administration of synthetic GCs.
Show more [+] Less [-]Which coastal and marine environmental contaminants are truly emerging? Full text
2015
Maruya, Keith A. | Dodder, Nathan G. | Tang, Chi-Li | Lao, Wenjian | Tsukada, David
To better understand the past and present impact of contaminants of emerging concern (CECs) in coastal and marine ecosystems, archived samples were analyzed for a broad suite of analytes, including pharmaceuticals and personal care products (PPCPs), flame retardants (including PBDEs), perfluorinated compounds (PFCs), and current-use pesticides. Surface sediment, mussels (Mytilus spp.) and sediment core samples collected from the California (USA) coast were obtained from environmental specimen banks. Selected CECs were detected in recent surface sediments, with nonylphenol (4-NP), its mono- and di-ethoxylates (NP1EO and NP2EO), triclocarban, and pyrethroid insecticides in the greatest abundance. Alkylphenols, triclocarban, and triclosan were present in sediment core segments from the 1970s, as well as in Mytilus tissue collected during the 1990s. Increasing concentrations of some CECs (e.g., miconazole, triclosan) were observed in the surface layers (ca. 2007) of a sediment core, in contrast to peak concentrations of 4-NP and triclocarban corresponding to input during the 1970s, and an apparent peak input for PBDEs during the 1990s. These results suggest that chemicals sometimes referred to as “emerging” (e.g., alkylphenols, triclocarban) have been present in the aquatic environment for several decades and are decreasing in concentration, whereas others (e.g., miconazole, triclosan) are increasing.
Show more [+] Less [-]Lead removal in rats using calcium alginate Full text
2015
Savchenko, Olga V. | Sgrebneva, Marina N. | Kiselev, Vladimir I. | Khotimchenko, Yuri S.
Lead (Pb) exposure, even at low levels, causes a variety of health problems. The aims of this study were to investigate the tissue distribution of lead in the bodies of rats, to evaluate lead removal from the internal organs and bones using calcium alginate in doses of 500, 200 and 100 mg/kg per day for 28 days and to assess the impact of calcium alginate on the level of essential elements. Lead (Pb), calcium (Ca), manganese (Mn), iron (Fe), copper (Cu) and zinc (Zn) levels in the blood, hearts, kidneys, livers and femurs of the experimental animals were measured using mass spectrometry with inductively coupled plasma. The results revealed that lead acetate exposure increased the levels of Pb in the blood and organs of the animals and significantly reduced contents of Ca, Mn, Fe, Cu and Zn. Treatment with calcium alginate in dose 500 mg/kg contributed to significant decreases in the amount of lead in the kidney, heart and bones of animals and a slight increase in the content of essential elements in the liver, kidneys and heart, although these changes were not significant. Decreasing of lead was not significant in the internal organs, bones and blood of animals treated with calcium alginate 200 and 100 mg/kg. Consequently, calcium alginate dose of 500 mg/kg more efficiently removes lead accumulated in the body. Calcium alginate does not have negative effect on level of essential elements quite the contrary; reducing the levels of lead, calcium alginate helps normalize imbalances of Ca, Mn, Fe, Cu and Zn. The results of this study suggest that calcium alginate may potentially be useful for the treatment and prevention of heavy metal intoxications.
Show more [+] Less [-]Enhancement of post-anoxic denitrification for biological nutrient removal: effect of different carbon sources Full text
2015
Chen, Hong-bo | Wang, Dong-bo | Li, Xiao Ming | Yang, Qi | Zeng, Guang-ming
Previous research has demonstrated that post-anoxic denitrification and biological nutrient removal could be achieved in the oxic/anoxic/extended-idle wastewater treatment regime. This study further investigated the effect of different carbon sources on post-anoxic denitrification and biological nutrient removal. Acetate, propionate (volatile fatty acids (VFAs)), glucose (carbohydrate), methanol, and ethanol (alcohol) were used as the sole carbon source, respectively. The experimental results showed that VFA substrates led to an improvement in nitrogen and phosphorus removal. The total nitrogen and phosphorus removal efficiency values driven by acetate achieved 93 and 99 %, respectively. In contrast, glucose present in mixed liquor deteriorated total nitrogen and phosphorus removal efficiency values to 72 and 54 %. In the reactors cultured with methanol and ethanol, 66 and 63 % of the total nitrogen were removed, and phosphorus removal efficiency values were 78 and 71 %, respectively. The mechanism studies revealed that different carbon sources affected the transformations of intracellular polyhydroxyalkanoates (PHAs) and glycogen. PHAs are the dominant storages for microorganisms cultured with VFA substrates. Though glycogen is not the favorable energy and carbon source for polyphosphate-accumulating organisms, it can be consumed by microorganisms related to biological nitrogen removal and is able to serve as the electron donor for post-anoxic denitrification.
Show more [+] Less [-]Combined effect of cadmium, lead, and UV rays on Bacillus cereus using comet assay and oxidative stress parameters Full text
2015
El-Sonbaty, S. M. | El-Hadedy, D. E.
Exposure to environmental chemicals and oxidative stress particularly at low dose levels may produce additive or synergistic interactions not seen in single component exposure. Exposure to cadmium, lead, and ultraviolet rays occurs in many occupational settings, such as pigment and battery production, galvanization, and recycling of electric tools. However, little is known about interactions between heavy metals and ultraviolet rays. This study aimed to evaluate the interactions of ultraviolet rays of 254 nm (UV-B) with cadmium or lead on Bacillus cereus. B. cereus was treated with different concentrations of cadmium or lead followed by exposure to UV-B radiation as combined effect. Photoirradiation of B. cereus with UV-B with exposure to cadmium or lead results in DNA damage, cytotoxicity, depletion of glutathione, and formation of lipid peroxidation. UV-B rays alone enhanced glutathione production which was depleted with lead and high doses of cadmium. Lead alone does not increase DNA breaking. The mechanism behind these interactions might be repair inhibition of oxidative DNA damage, since a decrease in repair capacity will increase susceptibility to reactive oxygen species generated by cadmium or lead. Lipid peroxidation was increased with exposure to UV-B and cadmium or lead. DNA, glutathione, and lipid peroxidation can be used as biomarkers to identify possible environmental contamination in bacteria. One conclusion from this model is the existence of more than multiplicative effects for co-exposures of cadmium or lead and UV rays.
Show more [+] Less [-]Arsenic removal from water employing a combined system: photooxidation and adsorption Full text
2015
Lescano, Maia | Zalazar, Cristina | Brandi, Rodolfo
A combined system employing photochemical oxidation (UV/H₂O₂) and adsorption for arsenic removal from water was designed and evaluated. In this work, a bench-scale photochemical annular reactor was developed being connected alternately to a pair of adsorption columns filled with titanium dioxide (TiO₂) and granular ferric hydroxide (GFH). The experiences were performed by varying the relation of As concentration (As (III)/As (V) weight ratio) at constant hydrogen peroxide concentration and incident radiation. Experimental oxidation results were compared with theoretical predictions using an intrinsic kinetic model previously obtained. In addition, the effectiveness of the process was evaluated using a groundwater sample. The mathematical model of the entire system was developed. It could be used as an effective tool for the design and prediction of the behaviour of these types of systems. The combined technology is efficient and promising for arsenic removal to small and medium scale.
Show more [+] Less [-]Impact of influent wastewater quality on nitrogen removal rates in multistage treatment wetlands Full text
2015
Gajewska, Magdalena | Jóźwiakowski, Krzysztof | Ghrabi, Ahmed | Masi, Fabio
Nitrogen removal in treatment wetlands is influenced by many factors, and the presence of electron donors (biodegradable organic matter) and electron acceptors (nitrate ions) is the main limiting one; for obtaining these conditions, multistage treatment wetlands (MTWs) are required, where an extensive nitrification can be obtained in the first stages under aerobic conditions leaving then to the following anoxic/anaerobic stages the duty of the denitrification. Most of the biodegradable organic matter is however oxidised in the first stages, and therefore, the inlet to the denitrification beds is usually poor of easily degradable carbon sources. This study is comparing the long-term performances obtained at several MTWs operating in Europe (North and South) and North Africa in order to understand if there is a significant avail in making use of the influent chemical oxygen demand (COD)/N ratio during the design phase for ensuring proper performances in terms of N overall removal. The statistic analysis performed in this study have shown that MTWs are capable to ensure sufficient removal of both organic and nutrients even in unfavourable proportions of macronutrients (C and N). The usual assumptions for conventional biological treatment systems concerning adequate C/N ratios seem to be dubious in case of wastewater treatment in MTWs.
Show more [+] Less [-]Pesticide residues in fruit samples: comparison of different QuEChERS methods using liquid chromatography–tandem mass spectrometry Full text
2015
Christia, C. | Bizani, E. | Christophoridis, C. | Fytianos, K.
Acetate- and citrate-buffered quick, easy, cheap, effective, rugged, safe (QuEChERS) pretreatment methods were evaluated for the determination of various pesticides in peaches, grapes, apples, bananas, pears, and strawberries from various regions of Greece, using LC-MS/MS. The purposes of this study were (i) to evaluate which type of QuEChERS method was the most appropriate and effective for each matrix; (ii) to apply the selected QuEChERS method for each matrix, in order to detect and quantify pesticide residues in various fruit samples using UPLC-MS/MS; (iii) to examine the concentration distribution of pesticide classes among fruit originating from various areas; and (iv) to assess pesticide concentration distribution between peel and flesh of fruit in order to evaluate the penetration of pesticide residues in the fruit flesh. Acetate-buffered QuEChERS was found to be the most suitable technique for most of the fruit matrices. According to the recovery values at two different concentration levels, peaches should preferably be treated by the citrate-buffered type, whereas grapes, bananas, apples, pears, and strawberries are best treated by the acetate-buffered version, although the differences in efficiency were small. The addition of graphitized carbon black significantly decreases the recovery of specific pesticides in all matrices except for strawberries. The majority of values do not exceed the official maximum residue levels set by the European Commission. Organophosphates proved to be the most commonly detected category along with triazines-triazoles-conazoles group and by carbamates. Apples and pears seem to be the most contaminated fruit matrices among those tested. Distribution of pesticide classes shows variations between different regions, suggesting different pesticide application practices. In the case of peaches and pears, there is an equal distribution of detected pesticides between peel and flesh, indicating penetration of contaminants into the fruit flesh.
Show more [+] Less [-]A comparison of the sublethal and lethal toxicity of four pesticides in Hyalella azteca and Chironomus dilutus Full text
2015
Hasenbein, Simone | Connon, Richard E. | Lawler, Sharon P. | Geist, Juergen
Laboratory toxicity testing is the primary tool used for surface water environmental risk assessment; however, there are critical information gaps regarding the sublethal effects of pesticides. In 10-day exposures, we assessed the lethal and sublethal (motility and growth) toxicities of four commonly used pesticides, bifenthrin, permethrin, cyfluthrin, and chlorpyrifos, on two freshwater invertebrates, Chironomus dilutus and Hyalella azteca. Pyrethroids were more toxic than the organophosphate chlorpyrifos in both species. Bifenthrin was most toxic to H. azteca survival and growth. Cyfluthrin was most toxic to C. dilutus. However, cyfluthrin had the greatest effect on motility on both H. azteca and C. dilutus. The evaluated concentrations of chlorpyrifos did not affect C. dilutus motility or growth, but significantly impacted H. azteca growth. Motility served as the most sensitive endpoint in assessing sublethal effects at low concentrations for both species, while growth was a good indicator of toxicity for all four pesticides for H. azteca. The integration of sublethal endpoints in ambient water monitoring and pesticide regulation efforts could improve identification of low-level pesticide concentrations that may eventually cause negative effects on food webs and community structure in aquatic environments.
Show more [+] Less [-]Occurrence and distribution of antibiotics in urban soil in Beijing and Shanghai, China Full text
2015
Gao, Lihong | Shi, Yali | Li, Wenhui | Liu, Jiemin | Cai, Yaqi
The recycling of reclaimed wastewater for irrigation and road cleaning is an important strategy to minimize water scarcity in megacities. However, little is known regarding the potential accumulation of antibiotics contained in reclaimed wastewater in urban soil. We investigated the occurrence and distribution of eight quinolones (QNs), nine sulfonamides (SAs), and five macrolides (MLs) antibiotics in urban surface soil in Beijing and Shanghai, China. QNs, especially norfloxacin (NOR), ofloxacin (OFL), and ciprofloxacin (CIP) were the predominant antibiotics in urban surface soil, and NOR revealed the highest average concentration of 94.6 μg kg⁻¹. The antibiotic concentrations in urban soil in our study were higher than those detected in agricultural soils after long-term wastewater irrigation and manure fertilization. The concentrations of antibiotics in Shanghai urban soil showed a significant negative correlation with soil pH and a positive correlation with total organic carbon (TOC), reflecting the effect of speciation and soil organic matter content on sorption and retention. In addition, antibiotic concentrations in the urban soil were positively correlated with heavy metal contents, likely due to their coexistence in reclaimed wastewater and the promoting effect of metals on the sorption of antibiotics. In several soil samples, NOR, OFL, CIP, enrofloxacin (ENR), and fleroxacin (FLE) showed higher concentrations than the trigger value of 100 μg kg⁻¹ in soil, indicating a potential risk for the environment.
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