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Chemical mimicking of bio-assisted aluminium extraction by Aspergillus niger’s exometabolites Full text
2016
Boriová, Katarína | Urík, Martin | Bujdoš, Marek | Pifková, Ivana | Matúš, Peter
Presence of microorganisms in soils strongly affects mobility of metals. This fact is often excluded when mobile metal fraction in soil is studied using extraction procedures. Thus, the first objective of this paper was to evaluate strain Aspergillus niger’s exometabolites contribution on aluminium mobilization. Fungal exudates collected in various time intervals during cultivation were analyzed and used for two-step bio-assisted extraction of alumina and gibbsite. Oxalic, citric and gluconic acids were identified in collected culture media with concentrations up to 68.4, 2.0 and 16.5 mmol L−1, respectively. These exometabolites proved to be the most efficient agents in mobile aluminium fraction extraction with aluminium extraction efficiency reaching almost 2.2%. However, fungal cultivation is time demanding process. Therefore, the second objective was to simplify acquisition of equally efficient extracting agent by chemically mimicking composition of main organic acid components of fungal exudates. This was successfully achieved with organic acids mixture prepared according to medium composition collected on the 12th day of Aspergillus niger cultivation. This mixture extracted similar amounts of aluminium from alumina compared to culture medium. The aluminium extraction efficiency from gibbsite by organic acids mixture was lesser than 0.09% which is most likely because of more rigid mineral structure of gibbsite compared to alumina. The prepared organic acid mixture was then successfully applied for aluminium extraction from soil samples and compared to standard single step extraction techniques. This showed there is at least 2.9 times higher content of mobile aluminium fraction in soils than it was previously considered, if contribution of microbial metabolites is considered in extraction procedures. Thus, our contribution highlights the significance of fungal metabolites in aluminium extraction from environmental samples, but it also simplifies the extraction procedure inspired by bio-assisted extraction of aluminium by common soil fungus A. niger.
Show more [+] Less [-]Isotopic evolution of atmospheric Pb from metallurgical processing in Flin Flon, Manitoba: Retrospective analysis using peat cores from bogs Full text
2016
Shotyk, W. | Rausch, N. | Outridge, P.M. | Krachler, M.
Atmospheric Pb deposition was reconstructed using peat cores from bogs in the vicinity of Flin Flon, Manitoba, Canada, home to a zinc refinery and copper smelter. The Sask Lake (SL4-1) core was collected 85 km NW of Flin Flon and Kotyk Lake (KOL) 30 km NE. The distribution of Sr and U show that both profiles are predominantly minerotrophic (ie groundwater-fed), but the Pb concentration profile shows that Pb was received exclusively from the atmosphere. Graphs of 208Pb/206Pb against 206Pb/207Pb document atmospheric Pb contamination dating from the early to mid-1800’s, well before the start of metallurgical processing (in 1930) and attributable to long-range atmospheric transport from other regions of North America. Industrial activities at Flin Flon clearly affected the concentrations, enrichment factor (calculated using Sc), and accumulation rates of Pb, but it is the similarity in isotopic composition, and contrast with crustal values (206Pb/207Pb ca. 1.20 to 1.22) which makes the connection to the Flin Flon ores. The KOL samples dating from 1925–1976 CE have a 206Pb/207Pb of 1.032 ± 0.002 (n = 11) which approach the values for the Flin Flon ores (206Pb/207Pb = 1.008). But even at SL4-1, the peat samples dating from 1925–1976 CE have a 206Pb/207Pb of 1.061 ± 0.022 (n = 18) which is well below the corresponding ratio of Canadian leaded gasoline (206Pb/207Pb = ca. 1.15). The SL4-1 site too, therefore, was clearly impacted by Pb from mining and metallurgy, despite the distance (88 km) from Flin Flon and being predominantly upwind. These two bogs not only provide the chronology of atmospheric Pb deposition for the past decades, but suggest that the extent of contamination may have been underestimated by previous studies.
Show more [+] Less [-]Towards the implementation of the Stockholm Convention in Spain: Five-year monitoring (2008–2013) of POPs in air based on passive sampling Full text
2016
Muñoz-Arnanz, Juan | Roscales, Jose L. | Ros, María | Vicente, Alba | Jiménez, Begoña
Within the framework of the Spanish monitoring program, this study reports on air concentration of DDTs, HCB, HCHs, NDL-PCBs, DL-PCBs, PCDD/Fs and PBDEs measured during the five-year sampling period 2008–2013. Spanish coastal remote and urban locations were studied using PUF disk passive air samplers which were deployed and collected every three months. Despite the wide range of concentrations measured for most contaminants, a common pattern of relative abundance (median values): NDL-PCBs (36.6 pg/m³) > HCB (24.8 pg/m³) ≈ HCHs (17.9 pg/m³) ≈ DDTs (16.6 pg/m³) > PBDEs (3.65 pg/m³) > DL-PCBs (2.99 pg/m³) >> PCDD/Fs (0.060 pg/m³) was found fairly consistent across most seasons and locations. Nevertheless, important variations in yearly concentrations were measured for different POPs. In general, higher levels of DDTs, HCHs, NDL-PCBs, DL-PCBs and PCDD/Fs were found in urban sites highlighting important differences between remote and urban sampling locations for most target contaminants. Greater concentrations of the banned organochlorine pesticides in urban locations suggested the existence of unexpected pointed sources that need to be further investigated and characterized. The limited dataset collected thus far rendered no clear temporal trends for most study target compounds, which emphasizes the necessity of the Spanish monitoring program future maintenance in time.
Show more [+] Less [-]Sorption of non-polar organic compounds by micro-sized plastic particles in aqueous solution Full text
2016
Hüffer, Thorsten | Hofmann, Thilo
The presence of microscale polymer particles (i.e., microplastics) in the environment has become a major concern in recent years. Sorption of organic compounds by microplastics may affect the phase distribution within both sediments and aqueous phases. To investigate this process, isotherms were determined for the sorption of seven aliphatic and aromatic organic probe sorbates by four polymers with different physico-chemical properties. Sorption increased in the order polyamide < polyethylene < polyvinylchloride < polystyrene. This order does not reflect the particle sizes of the investigated microplastics within the aqueous dispersions, indicating the influence of additional factors (e.g., π-π-interactions) on the sorption of aromatic compounds by polystyrene. Linear isotherms by polyethylene suggested that sorbate uptake was due to absorption into the bulk polymer. In contrast, non-linear isotherms for sorption by PS, PA, and PVC suggest a predominance of adsorption onto the polymer surface, which is supported by the best fit of these isotherms using the Polanyi-Manes model. A strong relationship between the sorption coefficients of the microplastics and the hydrophobicity of the sorbates suggests that hydrophobic interactions are of major importance.
Show more [+] Less [-]Maghemite nanoparticles and ferrous sulfate for the stimulation of iron plaque formation and arsenic immobilization in Phragmites australis Full text
2016
Pardo, Tania | Martínez-Fernández, Domingo | de la Fuente, Carlos | Clemente, Rafael | Komárek, Michael | Bernal, M Pilar
Wetland plants are considered as suitable biofilters for the removal of metal(loid)s and other contaminants from waters and wastewaters, due to their ability to accumulate and retain the contaminants in their roots. The iron plaque (IP) on the root surface influences the metal(loid)s retention processes. The stimulation of the IP development on roots of Phragmites australis by the external supply of a novel synthetic nanomaterial (nanomaghemite, nFe2O3) and FeSO4 (alone or in combination) was studied. An hydroponic experiment was carried out to evaluate the iron plaque formation after external iron addition, as well as their influence on arsenic immobilization capacity. Microscopic and spectroscopic techniques were utilized to assess the distribution of Fe and As in the roots. The addition of Fe stimulated the generation of the IP, especially when FeSO4 was involved. The nanoparticles alone were not efficient with regard to IP formation or As adsorption, even though they adhered to the root surface and did not enter into epithelial root cells. The combination of FeSO4 and nFe2O3 was the most effective treatment for improving the As removal capacity, and it seems to be an effective way to enhance the rhizofiltration potential of P. australis in As contaminated (waste)waters.
Show more [+] Less [-]Changes in leaf area, nitrogen content and canopy photosynthesis in soybean exposed to an ozone concentration gradient Full text
2016
Oikawa, Shimpei | Ainsworth, Elizabeth A.
Influences of ozone (O3) on light-saturated rates of photosynthesis in crop leaves have been well documented. To increase our understanding of O3 effects on individual- or stand level productivity, a mechanistic understanding of factors determining canopy photosynthesis is necessary. We used a canopy model to scale photosynthesis from leaf to canopy, and analyzed the importance of canopy structural and leaf ecophysiological characteristics in determining canopy photosynthesis in soybean stands exposed to 9 concentrations of [O3] (37–116 ppb; 9-h mean). Light intensity and N content peaked in upper canopy layers, and sharply decreased through the lower canopy. Plant leaf area decreased with increasing [O3] allowing for greater light intensity to reach lower canopy levels. At the leaf level, light-saturated photosynthesis decreased and dark respiration increased with increasing [O3]. These data were used to calculate daily net canopy photosynthesis (Pc). Pc decreased with increasing [O3] with an average decrease of 10% for an increase in [O3] of 10 ppb, and which was similar to changes in above-ground dry mass production of the stands. Absolute daily net photosynthesis of lower layers was very low and thus the decrease in photosynthesis in the lower canopy caused by elevated [O3] had only minor significance for total canopy photosynthesis. Sensitivity analyses revealed that the decrease in Pc was associated with changes in leaf ecophysiology but not with decrease in leaf area. The soybean stands were very crowded, the leaves were highly mutually shaded, and sufficient light for positive carbon balance did not penetrate to lower canopy leaves, even under elevated [O3].
Show more [+] Less [-]Microplastic interactions with freshwater microalgae: Hetero-aggregation and changes in plastic density appear strongly dependent on polymer type Full text
2016
Lagarde, Fabienne | Olivier, Ophélie | Zanella, Marie | Daniel, Philippe | Hiard, Sophie | Caruso, Aurore
In this study, the interactions between microplastics, chosen among the most widely used in industry such as polypropylene (PP) and high-density polyethylene (HDPE), and a model freshwater microalgae, Chlamydomas reinhardtii, were investigated. It was shown that the presence of high concentrations of microplastics with size >400 μm did not directly impact the growth of microalgae in the first days of contact and that the expression of three genes involved in the stress response was not modified after 78 days. In parallel, a similar colonization was observed for the two polymers. However, after 20 days of contact, in the case of PP only, hetero-aggregates constituted of microalgae, microplastics and exopolysaccharides were formed. An estimation of the hetero-aggregates composition was approximately 50% of PP fragments and 50% of microalgae, which led to a final density close to 1.2. Such hetero-aggregates appear as an important pathway for the vertical transport of PP microplastics from the water surface to sediment. Moreover, after more than 70 days of contact with microplastics, the microalgae genes involved in the sugar biosynthesis pathways were strongly over-expressed compared to control conditions. The levels of over-expression were higher in the case of HDPE than in PP condition. This work presents the first evidence that depending on their chemical nature, microplastics will follow different fates in the environment.
Show more [+] Less [-]Does cadmium affect the toxicokinetics of permethrin in Chironomus dilutus at sublethal level? Evidence of enzymatic activity and gene expression Full text
2016
Chen, Xin | Li, Huizhen | Zhang, Junjie | Ding, Yuping | Yau, Ching
Pyrethroids and metals were simultaneously detected in aquatic environment and showed antagonistic lethality to the benthic invertebrate, Chironomus dilutus. Accelerated biotransformation of pyrethroids in organism by the presence of metals was proposed as the likely reason for the antagonism. Mechanistic explanation for the role of toxicokinetics of pyrethroids in the antagonistic interaction would help better understanding the reasons for the joint toxicity. The goal was achieved in the current study by evaluating the impact of cadmium on toxicokinetic parameters of permethrin in C. dilutus, and by explaining the interaction through quantifying the activity and gene expression of biotransformation-related enzymes. Toxicokinetic parameters were simulated using a first-order kinetic model. Bioconcentration factors and uptake and elimination rate constants for permethrin were not significantly changed with the addition of cadmium at sublethal level, neither did the activity of enzymes, including glutathione S-transferase (GST), carboxylesterase (CarE), catalase and lipid peroxidation. Yet, the activities of metabolism-related enzymes (GST and CarE) showed an elevating tendency with adding cadmium. Furthermore, the expression of metabolism-related genes, including cytochrome P450 and glutathione S-transferase genes were significantly up-regulated in C. dilutus exposed to a mixture of permethrin and cadmium compared with permethrin only. Although co-exposure to cadmium did not induce toxicokinetic changes of permethrin in C. dilutus, it did enhance the activity of metabolic enzymes which were encoded by the metabolism-related genes, suggesting an acceleration of biotransformation of permethrin to less toxic metabolites in the midges. This possibly explained the antagonistic interaction for permethrin and cadmium.
Show more [+] Less [-]Evaluating real-world CO2 and NOX emissions for public transit buses using a remote wireless on-board diagnostic (OBD) approach Full text
2016
Yang, Liuhanzi | Zhang, Shaojun | Wu, Ye | Chen, Qizheng | Niu, Tianlin | Huang, Xu | Zhang, Shida | Zhang Liangjun, | Zhou, Yu | Hao, Jiming
The challenge to mitigate real-world emissions from vehicles calls for powerful in-use compliance supervision. The remote on-board diagnostic (OBD) approach, with wireless data communications, is one of the promising next-generation monitoring methods. We collected second-by-second profiles of carbon dioxide (CO2) and nitrogen oxides (NOX) emissions, driving conditions and engine performance for three conventional diesel and three hybrid diesel buses participating in a remote OBD pilot program in Nanjing, China. Our results showed that the average CO2 emissions for conventional diesel and hybrid diesel buses were 816 ± 83 g km−1 and 627 ± 54 g km−1, respectively, under a typical driving pattern. An operating mode binning analysis indicated that CO2 emissions reduction by series-parallel hybrid technology was largely because of the significant benefits of the technology under the modes of low speed and low power demand. However, significantly higher CO2 emissions were observed for conventional diesel buses during rush hours, higher than 1200 g km−1. The OBD data suggested no improvement in NOX emission reduction for hybrid buses compared with conventional buses; both were approximately 12 g km−1 because of poor performance of the selective catalyst reduction (SCR) systems in the real world. Speed-dependent functions for real-world CO2 and NOX emissions were also constructed. The CO2 emissions of hybrid buses were much less sensitive to the average speed than conventional buses. If the average speed decreased from 20 km h−1 to 10 km h−1, the estimated CO2 emission factor for conventional buses would be increased by 34%. Such a change in speed would increase NOX emissions for conventional and hybrid buses by 38% and 56%, respectively. This paper demonstrates the useful features of the remote OBD system and can inform policy makers how to take advantage of these features in monitoring in-use vehicles.
Show more [+] Less [-]The washout effects of rainfall on atmospheric particulate pollution in two Chinese cities Full text
2016
Guo, Ling-Chuan | Zhang, Yonghui | Lin, Hualiang | Zeng, Weilin | Liu, Tao | Xiao, Jianpeng | Rutherford, Shannon | Yau, Ching | Ma, Wenjun
Though rainfall is recognized as one of the main mechanisms to reduce atmospheric particulate pollution, few studies have quantified this effect, particularly the corresponding lag effect and threshold. This study aimed to investigate the association between rainfall and air quality using a distributed lag non-linear model. Daily data on ambient PM2.5 and PM2.5–10 (particulate matter with an aerodynamic diameter less than 2.5 μm and from 2.5 to 10 μm) and meteorological factors were collected in Guangzhou and Xi'an from 2013 to 2014. A better washout effect was found for PM2.5–10 than for PM2.5, and the rainfall thresholds for both particle fractions were 7 mm in Guangzhou and 1 mm in Xi'an. The decrease in PM2.5 levels following rain lasted for 3 and 6 days in Guangzhou and Xi'an, respectively. Rainfall had a better washout effect in Xi'an compared with that in Guangzhou. Findings from this study contribute to a better understanding of the washout effects of rainfall on particulate pollution, which may help to understand the category and sustainability of dust-haze and enforce anthropogenic control measures in time.
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