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Are there pharmaceutical compounds in sediments or in water? Determination of the distribution coefficient of benzodiazepine drugs in aquatic environment النص الكامل
2019
Nunes, Chalder Nogueira | dos Anjos, Vanessa Egéa | Quináia, Sueli Pércio
Alprazolam, clonazepam and diazepam are drugs belonging to the benzodiazepine class. These drugs might be important environmental contaminants in aquatic media. A total understanding of behavior and fate of drugs in aquatic environment is not available for these and other drugs. Thus, in this work, a complete optimization of sample treatment and extraction of analytes from sediments and water was described, as well a study of sediment/water distribution comparing it with sample characteristics. Ultrasound for 10 min and 3 steps using 3 mL of extraction solvent were chosen as the stirring form for extraction. A methanol/water (1:1) solution pH 12 was the best extraction solvent. Aiming to eliminate interferences, an addition of 10 μL of NaCl 3.06 mol L⁻¹ was necessary after each step of extraction. Sediment and water samples were characterized, presenting different values on physical-chemical parameters. Six distinct sample sets of water and sediments were spiked with each benzodiazepine and analyzed. Kd values varied from 1.4 to 9.2 L kg⁻¹ for clonazepam, 1.8–11.5 L kg⁻¹ for alprazolam and 2.31–12 L kg⁻¹ for diazepam. A principal component analysis showed high dependence on Kd with sample characteristics mainly related to sediments. In the systems, whose sediments presented high levels of clay, silt and organic matter, the drugs presented a great interaction with the solid part of the system, increasing the Kd value. Koc values varied from 149.25 to 634.13 L kg⁻¹ for clonazepam, 186.57–852.48 L kg⁻¹ for alprazolam, and 194.68–1189.81 L kg⁻¹ for diazepam.
اظهر المزيد [+] اقل [-]Spatio-temporal variations of shallow and deep well groundwater nitrate concentrations along the Indus River floodplain aquifer in Pakistan النص الكامل
2019
Khan, Shahrukh Nawaz | Yasmeen, Tahira | Riaz, Muhammad | Arif, Muhammad Saleem | Rizwan, Muhammad | Ali, Shafaqat | Tariq, Azeem | Jessen, Søren
Excessive use of nitrogenous fertilizers and their improper management in agriculture causes nitrate contamination of surface and groundwater resources. This study was conducted along the seasonally flooded alluvial agricultural area of Indus River Basin to determine the spatial and temporal dynamics of nitrate concentrations in the groundwater along the river. Total of 112 samples were collected from shallow (30–40 ft) and deep groundwater (120–150 ft) wells at seven sites, 25 km apart from each other and covered an area of 170 km along the river, during four sampling campaigns between October 2016 to May 2017 i.e. in start, mid and end of dry season. The study period covered the whole agricultural cycle including the wet summer season with no agricultural activities under flooding and the sampling sites were always less than 2 km from the river bank. Nitrate concentrations of shallow wells were 15–54 and 20–45 mg L⁻¹ during the start and middle of dry season, respectively. However, at the end of the dry season, the highest nitrate concentrations of 35–75 mg L⁻¹ were recorded and 70% of these samples contained nitrate concentrations above the permissible limit 50 mg L⁻¹. Similar seasonal patterns of nitrate concentrations were observed in deep wells, however, δ¹⁸O data suggested lower recharge in deep well than shallow wells. The results illustrated that high nitrate concentrations in shallow wells were associated with high δ¹⁸O values indicating that the quantity of evaporated water infiltrated from the floodplain, possibly from distribution channels, along with the nitrate polluting shallow wells more than the deep wells. At the end of the dry season, nitrate concentrations exceeded the permissible limits in both shallow and deep wells, which possibly happened due to the horizontal movement of groundwater along with the nitrate mixing during vertical seepage of river water to the aquifers.
اظهر المزيد [+] اقل [-]Spatial and temporal trends in poly- and per-fluorinated compounds in the Laurentian Great Lakes Erie, Ontario and St. Clair النص الكامل
2018
Codling, Garry | Sturchio, Neil C. | Rockne, Karl J. | Li, An | Peng, H. | Tse, Timothy J. | Jones, Paul D. | Giesy, John P.
The temporal and spatial trends in sediment of 22 poly- and perfluorinated (PFAS) compounds were investigated in the southern Great Lakes Erie and Ontario as well as Lake St. Clair. Surface concentrations measured by Ponar grab samples indicated a trend for greater concentrations near to urban sites. Mean concentrations ∑22PFAS were 15.6, 18.2 and 19 ng g−1 dm for Lakes St. Clair, Erie and Ontario, respectively. Perfluoro-n-butanoic acid (PFBA) and Perfluoro-n-hexanoic acid (PFHxA) were frequently determined in surface sediment and upper core samples indicating a shift in use patterns. Where PFBA was identified it was at relatively great concentrations typically >10 ng g−1 dm. However as PFBA and PFHxA are less likely to bind to sediment they may be indicative of pore water concentrations Sedimentation rates between Lake Erie and Lake Ontario differ greatly with greater rates observed in Lake Erie. In Lake Ontario, in general concentrations of PFAS observed in core samples closely follow the increase in use along with an observable change due to regulation implementation in the 1970s for water protection. However some of the more water soluble PFAS were observed in deeper core layers than the time of production could account for, indicating potential diffusion within the sediment. Given the greater sedimentation rates in Lake Erie, it was hoped to observe in greater resolution changes since the mid-1990s. However, though some decrease was observed at some locations the results are not clear. Many cores in Lake Erie had clearly observable gas voids, indicative of gas ebullition activity due to biogenic production, there were also observable mussel beds that could indicate mixing by bioturbation of core layers.
اظهر المزيد [+] اقل [-]Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model النص الكامل
2018
Wang, Yu | Guo, Hai | Zou, Shichun | Lyu, Xiaopu | Ling, Zhenhao | Cheng, Hairong | Zeren, Yangzong
A systematic field measurement was conducted at an island site (Wanshan Island, WSI) over the South China Sea (SCS) in autumn 2013. It was observed that mixing ratios of O₃ and its precursors (such as volatile organic compounds (VOCs), nitrogen oxides (NOₓ = NO + NO₂) and carbon monoxide (CO)) showed significant differences on non-episode days and episode days. Additional knowledge was gained when a photochemical box model incorporating the Master Chemical Mechanism (PBM-MCM) was applied to further investigate the differences/similarities of O₃ photochemistry between non-episode and episode days, in terms of O₃-precursor relationship, atmospheric photochemical reactivity and O₃ production. The simulation results revealed that, from non-O₃ episode days to episode days, 1) O₃ production changed from both VOC and NOₓ-limited (transition regime) to VOC-limited; 2) OH radicals increased and photochemical reaction cycling processes accelerated; and 3) both O₃ production and destruction rates increased significantly, resulting in an elevated net O₃ production over the SCS. The findings indicate the complexity of O₃ pollution over the SCS.
اظهر المزيد [+] اقل [-]Airborne ultrafine particles in a naturally ventilated metro station: Dominant sources and mixing state determined by particle size distribution and volatility measurements النص الكامل
2018
Mendes, Luís | Gini, Maria I. | Biskos, George | Colbeck, I. (Ian) | Eleftheriadis, Konstantinos
Ultrafine particle number concentrations and size distributions were measured on the platform of a metro station in Athens, Greece, and compared with those recorded at an urban background station. The volatility of the sampled particles was measured in parallel, providing further insights on the mixing state and composition of the sampled particles. Particle concentration exhibited a mean value of 1.2 × 10⁴ # cm⁻³ and showed a weak correlation with train passage frequency, but exhibited a strong correlation with urban background particle concentrations. The size distribution appears to be strongly influenced by outdoor conditions, such as the morning traffic rush hour and new particle formation events observed at noon. The aerosol in the metro was externally mixed throughout the day, with particle populations being identified (1) as fully refractory particles being more dominant during the morning traffic rush hours, (2) as core-shell structure particles having a non-volatile core coated with volatile material, and (3) fully volatile particles. The evolution of particle volatility and size throughout the day provide additional support that most nanoparticles in the metro station originate from outdoor urban air.
اظهر المزيد [+] اقل [-]Vertical profiles of lung deposited surface area concentration of particulate matter measured with a drone in a street canyon النص الكامل
2018
Kuuluvainen, Heino | Poikkimäki, Mikko | Järvinen, Anssi | Kuula, Joel | Irjala, Matti | Dal Maso, Miikka | Keskinen, Jorma | Timonen, Hilkka | Niemi, Jarkko V. | Rönkkö, Topi
The vertical profiles of lung deposited surface area (LDSA) concentration were measured in an urban street canyon in Helsinki, Finland, by using an unmanned aerial system (UAS) as a moving measurement platform. The street canyon can be classified as an avenue canyon with an aspect ratio of 0.45 and the UAS was a multirotor drone especially modified for emission measurements. In the experiments of this study, the drone was equipped with a small diffusion charge sensor capable of measuring the alveolar LDSA concentration of particles. The drone measurements were conducted during two days on the same spatial location at the kerbside of the street canyon by flying vertically from the ground level up to an altitude of 50 m clearly above the rooftop level (19 m) of the nearest buildings. The drone data were supported by simultaneous measurements and by a two-week period of measurements at nearby locations with various instruments. The results showed that the averaged LDSA concentrations decreased approximately from 60 μm2/cm3 measured close to the ground level to 36–40 μm2/cm3 measured close to the rooftop level of the street canyon, and further to 16–26 μm2/cm3 measured at 50 m. The high-resolution measurement data enabled an accurate analysis of the functional form of vertical profiles both in the street canyon and above the rooftop level. In both of these regions, exponential fits were used and the parameters obtained from the fits were thoroughly compared to the values found in literature. The results of this study indicated that the role of turbulent mixing caused by traffic was emphasized compared to the street canyon vortex as a driving force of the dispersion. In addition, the vertical profiles above the rooftop level showed a similar exponential decay compared to the profiles measured inside the street canyon.
اظهر المزيد [+] اقل [-]Diurnal variations and source apportionment of ozone at the summit of Mount Huang, a rural site in Eastern China النص الكامل
2017
Gao, J. | Zhu, B. | Xiao, H. | Kang, H. | Hou, X. | Yin, Y. | Zhang, L. | Miao, Q.
Comprehensive measurements were conducted at the summit of Mount (Mt.) Huang, a rural site located in eastern China during the summer of 2011. They observed that ozone showed pronounced diurnal variations with high concentrations at night and low values during daytime. The Weather Research and Forecasting with Chemistry (WRF-Chem) model was applied to simulate the ozone concentrations at Mt. Huang in June 2011. With processes analysis and online ozone tagging method we coupled into the model system, the causes of this diurnal pattern and the contributions from different source regions were investigated. Our results showed that boundary layer diurnal cycle played an important role in driving the ozone diurnal variation. Further analysis showed that the negative contribution of vertical mixing was significant, resulting in the ozone decrease during the daytime. In contrast, ozone increased at night owing to the significant positive contribution of advection. This shifting of major factor between vertical mixing and advection formed this diurnal variation. Ozone source apportionment results indicated that approximately half was provided by inflow effect of ozone from outside the model domain (O3-INFLOW) and the other half was formed by ozone precursors (O3-PBL) emitted in eastern, central, and southern China. In the O3-PBL, 3.0% of the ozone was from Mt. Huang reflecting the small local contribution (O3-LOC) and the non-local contributions (O3-NLOC) accounted for 41.6%, in which ozone from the southerly regions contributed significantly, for example, 9.9% of the ozone originating from Jiangxi, representing the highest geographical contributor. Because the origin and variation of O3-NLOC was highly related to the diurnal movements in boundary layer, the similar diurnal patterns between O3-NLOC and total ozone both indicated the direct influence of O3-NLOC and the importance of boundary layer diurnal variations in the formation of such distinct diurnal ozone variations at Mt. Huang.
اظهر المزيد [+] اقل [-]Seasonal variation in the nature of DOM in a river and drinking water reservoir of a closed catchment النص الكامل
2017
Awad, John | Leeuwen, John van | Chow, Christopher W.K. | Smernik, Ronald J. | Anderson, Sharolyn J. | Cox, Jim W.
Seasonal variation in the nature of DOM in a river and drinking water reservoir of a closed catchment النص الكامل
2017
Awad, John | Leeuwen, John van | Chow, Christopher W.K. | Smernik, Ronald J. | Anderson, Sharolyn J. | Cox, Jim W.
Dissolved organic matter (DOM) in surface waters used for drinking purposes can vary markedly in character depending on its source within catchments and the timing and intensity of rainfall events. Here we report the findings of a study on the character and concentration of DOM in waters collected during different seasons from Myponga River and Reservoir, South Australia. The character of DOM was assessed in terms of its treatability by enhanced coagulation and potential for disinfection by-product i.e. trihalomethane (THM) formation. During the wet seasons (winter and spring), water samples from the river had higher DOC concentrations (X¯: 21 mg/L) and DOM of higher average molecular weight (AMW: 1526 Da) than waters collected during the dry seasons (summer and autumn: DOC: 13 mg/L; AMW: 1385 Da). Even though these features led to an increase in the percentage removal of organics by coagulation with alum (64% for wet compared with 53% for dry season samples) and a lower alum dose rate (10 versus 15 mg alum/mg DOC removal), there was a higher THM formation potential (THMFP) from wet season waters (treated waters: 217 μg/L vs 172 μg/L). For reservoir waters, samples collected during the wet seasons had an average DOC concentration (X¯: 15 mg/L), percentage removal of organics by alum (54%), alum dose rates (13 mg/mg DOC) and THMFP (treated waters: 207 μg/L) that were similar to samples collected during the dry seasons (mean DOC: 15 mg/L; removal of organics: 52%; alum dose rate: 13 mg/mg DOC; THMFP: 212 μg/L for treated waters). These results show that DOM present in river waters and treatability by alum are highly impacted by seasonal environmental variations. However these in reservoir waters exhibit less seasonal variability. Storage of large volumes of water in the reservoir enables mixing of influent waters and stabilization of water quality.
اظهر المزيد [+] اقل [-]Seasonal variation in the nature of DOM in a river and drinking water reservoir of a closed catchment النص الكامل
2017
Awad, J. | van Leeuwen, J. | Chow, C. | Smernik, R. | Anderson, S. | Cox, J.
Abstract not available | John Awad, John van Leeuwen, Christopher W.K. Chow, Ronald J. Smernik, Sharolyn J. Anderson, Jim W. Cox
اظهر المزيد [+] اقل [-]A critical examination of the possible application of zinc stable isotope ratios in bivalve mollusks and suspended particulate matter to trace zinc pollution in a tropical estuary النص الكامل
2017
Araújo, Daniel | Machado, Wilson | Weiss, Dominik | Mulholland, Daniel S. | Boaventura, Geraldo R. | Viers, Jerome | Garnier, Jeremie | Dantas, Elton L. | Babinski, Marly
The application of zinc (Zn) isotopes in bivalve tissues to identify zinc sources in estuaries was critically assessed. We determined the zinc isotope composition of mollusks (Crassostrea brasiliana and Perna perna) and suspended particulate matter (SPM) in a tropical estuary (Sepetiba Bay, Brazil) historically impacted by metallurgical activities. The zinc isotope systematics of the SPM was in line with mixing of zinc derived from fluvial material and from metallurgical activities. In contrast, source mixing alone cannot account for the isotope ratios observed in the bivalves, which are significantly lighter in the contaminated metallurgical zone (δ66ZnJMC = +0.49 ± 0.06‰, 2σ, n = 3) compared to sampling locations outside (δ66ZnJMC = +0.83 ± 0.10‰, 2σ, n = 22). This observation suggests that additional factors such as speciation, bioavailability and bioaccumulation pathways (via solution or particulate matter) influence the zinc isotope composition of bivalves.
اظهر المزيد [+] اقل [-]Pervasive plastisphere: First record of plastics in egagropiles (Posidonia spheroids) النص الكامل
2017
Pietrelli, Loris | Di Gennaro, Alessia | Menegoni, Patrizia | Lecce, Francesca | Poeta, Gianluca | Acosta, Alicia T.R. | Battisti, Corrado | Iannilli, Valentina
The ability of Posidonia oceanica spheroids (egagropiles, EG) to incorporate plastics was investigated along the central Italy coast. Plastics were found in the 52.84% of the egagropiles collected (n = 685). The more represented size of plastics has range within 1–1.5 cm, comparable to the size of natural fibres. Comparing plastics occurring both in EG and in surrounding sand, Polyethylene, Polyester and Nylon were the most abundant polymers in EG, while PSE, PE, PP and PET were the most represented in sand. In particular PE and PP were significantly more represented in sand, while PE, Nylon, Polyester and microfibers (as pills) were more represented in EG. Within plastics found in EG, 26.9% were microfibers as small pills (<1 cm), mainly composed of polyamide, polyester, cotton and PET mixing. These microfibers might be produced by discharges from washing machines and currently represents an emerging pollutant with widespread distribution in marine and freshwater ecosystems.
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