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In vitro tools for the toxicological evaluation of sediments and dredged materials: intra- and inter-laboratory comparisons of chemical and bioanalytical methods Full text
2018
Eichbaum, Kathrin | Brinkmann, Markus | Nuesser, Leonie | Gembé, Carolin | Ohlig, Marina | Buchinger, Sebastian | Reifferscheid, Georg | Hecker, Markus | Giesy, John P. | Hollert, Henner
The implementation of in vitro bioassays for the screening of dioxin-like compounds (DLCs) into management guidelines of dredged material is of increasing interest to regulators and risk assessors. This study reports on an intra- and inter-laboratory comparison study between four independent laboratories. A bioassay battery consisting of RTL-W1 (7-ethoxy-resorufin-O-deethylase; EROD), H4IIE (micro-EROD), and H4IIE-luc cells was used to assess aryl hydrocarbon receptor-mediated effects of sediments from two major European rivers, differently contaminated with DLCs. Each assay was validated by characterization of its limit of detection (LOD) and quantification (LOQ), z-factor, reproducibility, and repeatability. DLC concentrations were measured using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and compared to bioassay-specific responses via toxicity equivalents (TEQs) on intra- and inter-laboratory levels. The micro-EROD assay exhibited the best overall performance among the bioassays. It was ranked excellent (z-factor = 0.54), reached a repeatability > 75%, was highly comparable (r ² = 0.87) and reproducible (83%) between two laboratories, and was well correlated (r ² = 0.803) with TEQs. Its LOD and LOQ of 0.5 and 0.7 pM 2,3,7,8-TCDD, respectively, approached LOQs of HRGC/HRMS measurements. In contrast, cell lines RTL-W1 and H4IIE-luc produced LODs > 0.7 pM 2,3,7,8-TCDD, LOQs > 1.7 pM 2,3,7,8-TCDD, and repeatability < 70%. Based on the data obtained, the micro-EROD assay is the most favorable bioanalytical tool, and via a micro-EROD-based limit value, it would allow for the assessment of sediment DLC concentrations; thus, it could be considered for the implementation into testing and management guidelines for dredged materials.
Show more [+] Less [-]Spatial distribution of metals within the liver acinus and their perturbation by PCB126 Full text
2018
Klaren, William D. | Vine, David | Vogt, Stefan | Robertson, Larry W.
Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.
Show more [+] Less [-]Bismuth vanadate-based semiconductor photocatalysts: a short critical review on the efficiency and the mechanism of photodegradation of organic pollutants Full text
2018
Monfort, Olivier | Plesch, Gustav
The number of publications on photocatalytic bismuth vanadate-based materials is constantly increasing. Indeed, bismuth vanadate is gaining stronger interest in the photochemical community since it is a solar-driven photocatalyst. However, the efficiency of BiVO₄-based photocatalyst under sunlight is questionable: in most of the studies investigating the photodegradation of organic pollutants, only few works identify the by-products and evaluate the real efficiency of BiVO₄-based materials. This short review aims to (i) present briefly the principles of photocatalysis and define the photocatalytic efficiency and (ii) discuss the formation of reactive species involved in the photocatalytic degradation process of pollutants and thus the corresponding photodegradation mechanism could be determined. All these points are developed in a comprehensive discussion by focusing especially on pure, doped, and composite BiVO₄. Therefore, this review exhibits a critical overview on different BiVO₄-based photocatalytic systems with their real efficiency. This is a necessary knowledge for potential implementation of BiVO₄ materials in environmental applications at larger scale than laboratory conditions.
Show more [+] Less [-]Heavy metal and δ13C value variations and characterization of dissolved organic matter (DOM) during vermicomposting of pig manure amended with 13C-labeled rice straw Full text
2018
Zhu, Weiqin | Yao, Wu | Shen, Xuyang | Zhang, Weiwen | Xu, Huiting
In this work, a mixture of pig manure and ¹³C-labeled rice straw was vermicomposted with Eisenia fetida for 40 days. The results showed that after they acclimated to the vermicomposting environment, the earthworms helped to degrade the substrate residues. After 40 days, the vermicomposting led to much higher pH, EC, C/N, available K, available P, available Zn, and CEC values but much lower available N and available Cu values in the substrate residues compared to the initial values. The earthworms accumulated ¹³C, Cu, and Zn with a heavy metal enrichment capacity in the order of Cu > Zn. Furthermore, the correlation analysis showed that the Cu and Zn content in the DOM was mainly controlled by the Cu and Zn content in the pig manure. The earthworms accumulated Cu and Zn by feeding on the substrate residues, but the DOM from the ¹³C-labeled rice straw helped to extract Zn from the substrate residues and promoted the migration of Zn into the earthworm tissues and/or DOM. Moreover, the characterization of the DOM extracted from the substrate residues revealed a decrease in the content of the aliphatic alcohols or polysaccharide-like substances and an increase in the aromatic compounds and fulvic or humic acid-like substances in the DOM as the vermicomposting time increased. This indicated that the higher humification degree in the DOM caused by vermicomposting contributed to the increased mobility of Zn in the substrate residues and helped Zn migrate into the earthworms or DOM.
Show more [+] Less [-]Evaluation of (–)-borneol derivatives against the Zika vector, Aedes aegypti and a non-target species, Artemia sp Full text
2018
Nunes, Rafaela K. V. | Martins, Ulisses N. | Brito, Thaysnara B. | Nepel, Angelita | Costa, Emmanoel V. | Barison, Andersson | Santos, Roseli L. C. | Cavalcanti, Sócrates C. H.
Zika, dengue, and chikungunya are vector-borne diseases of pronounced concern transmitted by the mosquito Aedes aegypti Linn. (Diptera: Culicidae). The most important method to avoid outbreaks is to control mosquito spreading by the employment of insecticides and larvicides. Failure to control mosquito dispersal is mostly accounted to Ae. aegypti resistance to currently available larvicides and insecticides, encouraging the development of novel pesticides. In addition, the excessive use of larvicides poses serious threats to human health and the environment. Evaluation of natural products as larvicides in an attempt to overcome this situation is often found in the literature because products originated from nature are considered less toxic to non-target species and more eco-friendly. (–)-Borneol is a bicyclic monoterpene present in essential oils with moderate larvicidal activity. On account of these facts, it was of our interest to synthesize (–)-borneol ester derivatives aiming to study its structure-activity relationships against Ae. aegypti larvae. With the goal to estimate toxicity to a non-target species, evaluation of the lethal concentration 50% (LC₅₀) on Artemia sp. (Artemiidae) and calculation of selectivity towards Ae. aegypti were carried out. The most potent derivative, (–)-Bornyl chloroacetate, exhibited the highest suitability index, demonstrating lower environmental toxicity than other borneol ester derivatives. A parabolic relationship between (–)-borneol esters larvicidal activity and partition coefficient (Log P) was achieved and a correlation equation obtained, validating the importance of lipophilicity to the larvicidal activity of these compounds.
Show more [+] Less [-]A review on removal of siloxanes from biogas: with a special focus on volatile methylsiloxanes Full text
2018
Shen, Maocai | Zhang, Yaxin | Hu, Duofei | Fan, Jinshi | Zeng, Guangming
The occurrence of siloxanes is a major barrier to use of biogas as renewable energy source, and removal of siloxanes from biogas before combustion is needed. The siloxane can be transformed into silicon dioxide (SiO₂) through the combustion process in engine, which will be deposited on the spark plug, cylinder, and impeller to form the silica layer, causing the wear and damage of the engine parts, and shorten the life of the engine and affect the utilization efficiency of the biogas. This paper reviewed some methods and technologies for siloxanes removal from biogas. There are three commercial available technologies to remove siloxanes: adsorption, absorption, and cryocondensation. Other newer technologies with better prospects for development also have made a research progress, including membrane, catalysts, biotrickling filters. This work introduces the source and characterization of siloxanes in biogas, reviews the scientific progress of siloxanes removal, and discusses the development direction and further research of removal siloxanes.
Show more [+] Less [-]Increased leaching and addition of amendments improve the properties of seawater-neutralized bauxite residue as a growth medium Full text
2018
Li, Yaying | Haynes, Richard J. | Chandrawana, Irena | Zhou, Ya-Feng
Laboratory and greenhouse experiments were carried out to investigate the chemical, physical, and microbial properties of seawater-neutralized bauxite residues and the effects of additional leaching (1 pore volume of deionized water versus an additional 6 pore volumes) and amendment with gypsum (5%) and/or cattle manure (6%) on its properties and on the growth of Rhodes grass (Chloris gayana). Additional leaching resulted in a decrease in EC, exchangeable Na, SAR, and ESP. For unamended control treatments, additional leaching induced a rise in pHSE from 8.5 to 9.6 and pH₁:₅ from 9.1 to 10.1 due to dissolution of residual alkalinity. Addition of gypsum arrested this pH increase resulting in a final pHSE of 7.5 and pH₁:₅ of 8.8. In control treatments, additional leaching resulted in a pronounced decrease in Rhodes grass yields. However, in gypsum and cattle manure-amended treatments, it led to substantial yield increases and decreases in tissue Al and Na concentrations and increased K/Na ratios. Upon drying for the first time, bauxite residue was shown to contract and form a solid massive structure. The aggregates formed from crushing this material were water stable (as measured by wet sieving). Additions of cattle manure or gypsum to residue aggregates did not affect pore size distribution. Addition of cattle manure increased organic C and microbial biomass C content and basal respiration rate while additional leaching increased basal respiration and metabolic quotient. It was concluded that a combination of drying and crushing the residue, amending it with gypsum and organic manure followed by extensive leaching results in the formation of a medium that supports plant growth.
Show more [+] Less [-]Different pathways of nitrogen and phosphorus regeneration mediated by extracellular enzymes in temperate lakes under various trophic state Full text
2018
Song, Chunlei | Cao, Xiuyun | Zhou, Yiyong | Azzaro, Maurizio | Monticelli, Luis Salvador | Leonardi, Marcella | La Ferla, Rosabruna | Caruso, Gabriella
Several Italian and Chinese temperate lakes with soluble reactive phosphorus concentrations < 0.015 mg L⁻¹ were studied to estimate nitrogen and phosphorus regeneration mediated by microbial decomposition and possible different mechanisms driven by prevailing oligo- or eutrophic conditions. Leucine aminopeptidase (LAP), beta-glucosidase (GLU) and alkaline phosphatase (AP), algal, and bacterial biomass were related to trophic and environmental variables. In the eutrophic lakes, high algal and particulate organic carbon concentrations stimulated bacterial respiration (> 20 μg C L⁻¹ h⁻¹) and could favor the release of inorganic phosphorus. High extracellular enzyme activities and phosphorus solubilizing bacteria abundance in sediments accelerated nutrient regeneration. In these conditions, the positive GLU-AP relationship suggested the coupling of carbon and phosphorus regeneration; an efficient phosphorus regeneration and high nitrogen levels (up to 0.067 and 0.059 mg L⁻¹ NH₄ and NO₃ in Italy; 0.631 and 1.496 mg L⁻¹ NH₄ and NO₃ in China) led to chlorophyll a peaks of 14.9 and 258.4 μg L⁻¹ in Italy and China, respectively, and a typical algal composition. Conversely, in the oligo-mesotrophic lakes, very low nitrogen levels (in Italy, 0.001 and 0.005 mg L⁻¹ NH₄ and NO₃, respectively, versus 0.053 and 0.371 mg L⁻¹ in China) induced high LAP, while low phosphorus (33.6 and 46.3 μg L⁻¹ total P in Italy and China, respectively) led to high AP. In these lakes, nitrogen and phosphorus regeneration were coupled, as shown by positive LAP-AP relationship; however, the nutrient demand could not be completely met without the supply from sediments, due to low enzymatic activity and phosphorus solubilizing bacteria found in this compartment.
Show more [+] Less [-]Baccharis dracunculifolia (Asteraceae) essential oil toxicity to Culex quinquefasciatus (Culicidae) Full text
2018
Alves, Kyvia F. | Caetano, Flávio H. | Pereira Garcia, Israel J. | Santos, Hérica L. | Silva, Denise B. | Siqueira, João M. | Tanaka, Aparecida S. | Alves, Stênio N.
The control of mosquitoes by means of chemical insecticides has been a problem, mainly due to the possibility of resistance developed by insects to xenobiotics. For this reason, demand for botanical insecticides has increased. In this sense, the present work aims to verify the susceptibility and morphological and biochemical alterations of Culex quinquefasciatus larvae after exposure to essential oil (EO) of leaves of Baccharis dracunculifolia. To observe the larvicidal action, larvae were exposed to EO at concentrations of 25, 50, 100, and 200 mg/L, until their emergence to adults. The control group was exposed to deionized water and dimethyl sulfoxide. Morphological analyses were also carried out using hematoxylin and eosin, mercury bromophenol blue, Nile blue, and periodic acid Schiff. Biochemical analyses of total glucose, triacylglyceride (TAG), protein, and acetylcholinesterase levels were performed. The phytochemical analysis of the EO showed (E)-nerolidol as the major compound (30.62%). Larvae susceptibility results showed a LC₅₀ of 34.45 mg/L for EO. Morphological analysis showed that there were histological changes in midgut. For biochemical analyses, the glucose level in the larvae exposed to EO for 24 h decreased significantly, unlike the TAG levels, which increased. The total protein level of the larvae also increased after exposure for 24 h, and acetylcholinesterase levels decreased significantly. Taking all our data into account, we can conclude that EO causes destabilization in larva, leading to histological changes, metabolic deregulation and, consequently, their death.
Show more [+] Less [-]Characteristics of polycyclic aromatic hydrocarbons in PM2.5 emitted from different cooking activities in China Full text
2018
Li, Yun-Chun | Qiu, Jia-Qian | Shu, Man | Ho, Steven Sai Hang | Cao, Jun-Ji | Wang, Ge-Hui | Wang, Xian-Xiang | Zhao, Xiao-Qing
Nineteen polycyclic aromatic hydrocarbons (PAHs) in PM₂.₅ emitted from five different cooking activities were characterized, and their influencing factors were determined. The total quantified particle-bounded PAH concentrations (ΣPAHs) in the airs from the cooking activities were 4.2–36.5-fold higher than those in corresponding backgrounds. The highest ΣPAHs were seen in cafeteria frying (783 ± 499 ng/m³), followed by meat roasting (420 ± 191 ng/m³), fish roasting (210 ± 105 ng/m³), snack-street boiling (202 ± 230 ng/m³), and cafeteria boiling (150 ± 65 ng/m³). The main influencing factors on the PAH emissions were cooking methods, fat contents in raw materials, and oil consumptions. Four- to six-ringed PAHs had the highest contributions to the ΣPAHs (avg. 87.5%). Diagnostic ratios of individual PAH were similar between the two charbroiling and other three conventional Chinese cooking methods, respectively, demonstrating the dominance of cooking methods in the PAH emissions. Remarkably high benzo(b)fluoranthene/benzo(k)fluoranthene (BbF/BkF) ratio (8.31) was seen in the snack-street boiling, attributed to the coal combustion as cooking fuel. Both fluoranthene/(fluoranthene + pyrene) [FLT/(FLT + PYR)] and benzo(a)anthracene/(benzo(a)anthracene + chrysene) [BaA/(BaA + CHR)] ratios were higher for the oil-based cooking than those from the water-based ones. In addition, two ratios of indeno(1,2,3-cd)pyrene/(indeno(1,2,3-cd)pyrene + benzo(g,h,i)perylene) [IPY/(IPY + BPE)] and benzo(a)pyrene/(benzo(a)pyrene + benzo(g,h,i)perylene) [BaP/(BaP + BPE)] were higher for two charbroiling than the three conventional Chinese cooking methods. The characterization work in this study is particularly important since cooking is a potential contributor of atmospheric PAHs in urban China. Carcinogenic potencies of PAHs were assessed by comparison with the air quality guideline and health risk estimation. The BaP and BaP equivalent were higher for the oil-based than the water-based cooking activities.
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