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Are there pharmaceutical compounds in sediments or in water? Determination of the distribution coefficient of benzodiazepine drugs in aquatic environment
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.
Show more [+] Less [-]Comparative health risk assessment of in-vehicle exposure to formaldehyde and acetaldehyde for taxi drivers and passengers: Effects of zone, fuel, refueling, vehicle's age and model
2019
This study aimed to assess the carcinogenic and non-carcinogenic risks of in-vehicle exposure in Tehran, Iran to formaldehyde and acetaldehyde for different models of taxis, and to explore the effects of city zone, taxi vehicle type, the taxi's age (<1, 1–5, 5–10), fuel type (gasoline, CNG, and LPG), and refueling activities on the estimated health risks based on previously measured concentrations. The overall and age-specific carcinogenic and non-carcinogenic risks of these compounds for taxi drivers and passengers were estimated separately using Monte Carlo simulations. Three scenarios of exposure frequency were defined for taxis commuting in different zones of city: Restricted Traffic Zone (RTZ) and Odd-Even Zone (OEZ) as two plans to reduce air pollution, and no-restriction zone (NRZ). The carcinogenic risks for drivers and passengers, the average risks of formaldehyde and acetaldehyde for most cases were above the 1 × 10⁻⁴. The health risks were greater in Restricted Traffic Zone (RTZ) and Odd-Even Zone (OEZ) in comparison to no-restriction zone (NRZ). The carcinogenic risk from formaldehyde exposures were higher than those for acetaldehyde in all cases. Taxis fueled with LPG showed lower cancer risks for both acetaldehyde and formaldehyde. Refueling increased the carcinogenic risk from both compounds. For non-carcinogenic risks from acetaldehyde, the average hazard ratios for both drivers and passengers were >1, indicating a non-negligible risk. Cancer and non-cancer risks for the taxi drivers were greater than the passengers given the higher time of occupancy. The present study showed that transportation in taxis can impose significant long-term health risks to both passengers and drivers. Development and investment in cleaner choices for public transportations are required.
Show more [+] Less [-]Performance of a novel magnetic solid-phase-extraction microsphere and its application in the detection of organic micropollutants in the Huai River, China
2019
Solid phase extraction has been increasingly applied for the detection of organic micropollutants (OMPs). However, time-consuming and high-cost disadvantages also limit the widespread use of this method, especially for the extraction of large-volume field water samples. In this study, a gas chromatography-mass spectrometry (GC-MS) method based on the magnetic microsphere (M150) solid-phase-extraction (MSPE) was established to investigate the OMPs in source water throughout the whole Huai River. In brief, the results demonstrated that the extraction efficiency of the M150 was superior to that of C₁₈ and HLB for the selected OMPs, including species of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), phthalate esters (PAEs) and nitrobenzenes (NBs), and the method detection limits of M150 for these OMPs were comparable to those of C₁₈ and HLB. The optimized conditions of extraction and elution were the 100 mg/L dosages of microspheres, extraction time of 60 min and pH of 2, and the eluent with a similar polarity, hydrophobicity and molecular structure to the OMPs rendered higher elution efficiencies. A total of 21 types of OMPs affiliating to PAHs, OCPs, PAEs and NBs were detected by the established method, with the total concentrations of 505–2310 ng/L in source water of the Huai River. Spatial differences of the OMPs were also observed, demonstrating the link between pollutant profiles and geographical locations. This study provides an alternative to enrich OMPs in filed water samples, and it reveals pollutant profiles of source water throughout the whole Huai River.
Show more [+] Less [-]Enhanced photocatalytic degradation of methyl orange by porous graphene/ZnO nanocomposite
2019
Degrading aquatic organic pollutants efficiently is very important but strongly relied on the design of photocatalysts. Porous graphene could increase photocatalytic performance of ZnO nanoparticles by promoting the effective charge separation of electron-hole pairs if they can be composited. Herein, porous graphene, ZnO nanoparticles and porous graphene/ZnO nanocomposite were prepared by fine tuning of partial combustion, which graphene oxide imperfectly covered by the layered Zn salt was combusted under muffle furnace within few minutes. Resulting ZnO nanoparticles (32–72 nm) are dispersed uniformly on the surface of graphene sheets, the pore sizes of porous graphene are in the range from ∼3 to ∼52 nm. The synthesized porous graphene/ZnO nanocomposite was confirmed to show enhanced efficiency under natural sunlight irradiation compared with pure ZnO nanoparticles. Using porous graphene/ZnO nanocomposite, 100% degradation of methyl orange can be achieved within 150 min. The synergetic effect of photocatalysis and adsorption is main reason for excellent MO degradation of PG/ZnO nanocomposite. This work may offer a new route to accurately prepare porous graphene-based nanocomposite and open a door of their applications.
Show more [+] Less [-]Phosphorus (P) release risk in lake sediment evaluated by DIFS model and sediment properties: A new sediment P release risk index (SPRRI)
2019
Wu, Zhihao | Wang, Shengrui | Ji, Ningning
A new sediment P release risk index (SPRRI) for “in-situ” phosphorus (P) release risk in lake sediment, is developed based on diffusive gradients in thin films (DGT) technique, DGT induced flux in sediments (DIFS) model and sediment properties. SPRRI includes three sub-indexes, which contain (1) the labile P pool size, (2) resupply constant (r) and desorption rate (Dspt rate) for P transfer and (3) the molar ratio between iron (Fe) in sequential extraction for sediment P by bicarbonate-dithionite (BD) and aluminum (Al) by NaOH (at 25 °C), i.e. BD(Fe)/Al[NaOH25] in sediment solid. The first sub-index considers P release from (i) sediment with NH₄Cl-P+BD-P pool, i.e. the loosely sorbed P (NH₄Cl-P) plus iron associated P (BD-P), or (ii) sediment with NH₄Cl-P pool, respectively. The second and third sub-indexes reflect kinetic P desorption and resupply ability of solid phase, and the effect of P sequestration by Al hydroxide on P release, in turn. The inner relationship between SPRRI and sub-indexes, and their effects on P release risk are elucidated. SPRRI can be used to evaluate sediment P reactivity by five release risk ranks. For Lake Dianchi (China), P transfer dynamics, labile P pool, resupply ability and Al-P in sediment, and “external P-loading” control and affect P release risk in different regions, which is reflected by the spatial distribution map for SPRRI. The present SPRRI can be applied for lakes with (1) pH range varying from moderate acidity to weak alkalinity in waterbody and (2) NH₄Cl-P or NH₄Cl-P+BD-P pool in sediment solid.
Show more [+] Less [-]Potential phytomanagement of military polluted sites and biomass production using biofuel crop miscanthus x giganteus
2019
Pidlisnyuk, Valentina | Erickson, Larry | Stefanovska, Tatyana | Popelka, Jan | Hettiarachchi, Ganga | Davis, Lawrence | Trögl, Josef
This study aims to summarize results on potential phytomanagement of two metal(loid)-polluted military soils using Miscanthus x giganteus. Such an option was tested during 2-year pot experiments with soils taken from former military sites in Sliač, Slovakia and Kamenetz-Podilsky, Ukraine. The following elements were considered: As, Cu, Fe, Mn, Pb, Sr, Ti, Zn and Zr. M. x giganteus showed good growth at both military soils with slightly higher maximum shoot lengths in the second year of vegetation. Based on Principal Component Analysis similarities of metal(loid) uptake by roots, stems and leaves were summarized. Major part of the elements remained in M. x giganteus roots and rather limited amounts moved to the aerial parts. Levels taken up decreased in the second vegetation year. Dynamics of foliar metal(loid) concentrations divided the elements in two groups: essential elements required for metabolism (Fe, Mn, Cu, and Zn) and non-essential elements without any known metabolic need (As, Sr, Ti, and Zr). Fe, Mn, Ti and Sr showed similar S-shaped uptake curve in terms of foliar concentrations (likely due to dilution in growing biomass), while Cu exhibited a clear peak mid-season. Behavior of Zn was in between. Foliar Zr and As concentrations were below detection limit. The results illustrated a good potential of M. x giganteus for safely growing on metal-polluted soils taken from both military localities.
Show more [+] Less [-]Impacts of peat-forest smoke on urban PM2.5 in the Maritime Continent during 2012–2015: Carbonaceous profiles and indicators
2019
This study characterizes impacts of peat-forest (PF) smoke on an urban environment through carbonaceous profiles of >260 daily PM₂.₅ samples collected during 2012, 2013 and 2015. Organic carbon (OC) and elemental carbon (EC) comprising eight carbonaceous fractions are examined for four sample groups – non-smoke-dominant (NSD), smoke-dominant (SD), episodic PM₂.₅ samples at the urban receptor, and near-source samples collected close to PF burning sites. PF smoke introduced much larger amounts of OC than EC, with OC accounting for up to 94% of total carbon (TC), or increasing by up to 20 times in receptor PM₂.₅. SD PM₂.₅ at the receptor site and near-source samples have OC3 and EC1 as the dominant fractions. Both sample classes also exhibit char-EC >1.4 times of soot-EC, characterizing smoldering-dominant PF smoke, unlike episodic PM₂.₅ at the receptor site featuring large amounts of pyrolyzed organic carbon (POC) and soot-EC. Relative to the mean NSD PM₂.₅ at the receptor, increasing strength of transboundary PF smoke enriches OC3 and OC4 fractions, on average, by factors of >3 for SD samples, and >14 for episodic samples. A peat-forest smoke (PFS) indicator, representing the concentration ratio of (OC2+OC3+POC) to soot-EC, shows a temporal trend satisfactorily correlating with an organic marker (levoglucosan) of biomass burning. The PFS indicator systematically differentiates influences of PF smoke from source to urban receptor sites, with a progressive mean of 3.6, 13.4 and 20.1 for NSD, SD and episodic samples respectively at the receptor site, and 54.7 for the near-source PM₂.₅. A PFS indicator of ≥5.0 is proposed to determine dominant influence of transboundary PF smoke on receptor urban PM₂.₅ in the equatorial Asia with ∼90% confidence. Assessing >2900 hourly OCEC data in 2017–2018 supports the applicability of the PFS indicator to evaluate hourly impacts of PF smoke on receptor urban PM₂.₅ in the Maritime Continent.
Show more [+] Less [-]Response of sediment bacterial community to triclosan in subtropical freshwater benthic microcosms
2019
The response of sediment bacterial communities in subtropical freshwater benthic microcosms to sediment-associated triclosan (TCS; 28 d exposure) was analysed using Illumina high-throughput sequencing. This study highlights the interactive effects of TCS and the presence of benthic macroinvertebrates (Limnodrilus hoffmeisteri and Viviparidae bellamya) on sediment bacterial communities. Our results show that TCS alone significantly altered the taxonomic composition and decreased alpha diversity of sediment bacterial communities at concentrations ≥80 μg TCS/g dry weight (dw) sediment (sed). Regarding dominant phyla, TCS significantly reduced the relative abundance of Bacteroidetes and Firmicutes at these concentrations, whereas the relative abundance of Chloroflexi and Cyanobacteria increased. In the presence of benthic macroinvertebrates, the sediment bacterial community was affected by 8 μg TCS/g dw sed as well. However, the presence of benthic macroinvertebrates did not cause measurable changes to bacterial community in unspiked (i.e., control) sediment. These results indicate that TCS alone would not alter the sediment bacterial community at environmentally relevant concentrations (up till 8 μg/g dw sed), but may have an effect in combination with the presence of benthic macroinvertebrates. Therefore, we recommend to include benthic macroinvertebrates when assessing the response of sediment bacterial communities during exposure to environmental stress such as organic contaminants.
Show more [+] Less [-]Sorption of pentachlorophenol and phenanthrene by humic acid-coated hematite nanoparticles
2019
Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HAₚₑₐₜ) and soil humic acid (HAₛₒᵢₗ) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HAₚₑₐₜ-hematite NPs showed higher sorption affinity for both PCP and PHE than HAₛₒᵢₗ-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HAₚₑₐₜ-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).
Show more [+] Less [-]CO2, CO, hydrocarbon gases and PM2.5 emissions on dry season by deforestation fires in the Brazilian Amazonia
2019
Amaral, Simone Simões | Costa, Maria Angélica Martins | Soares Neto, Turibio Gomes | Costa, Marillia Pereira | Dias, Fabiana Ferrari | Anselmo, Edson | Santos, José Carlos dos | Carvalho, João Andrade de
The rate of deforestation in Brazil increased by 29% between 2015 and 2016, resulting in an increase of greenhouse gas emissions (GHG) of 9%. Deforestation fires in the Amazonia are the main source of GHG in Brazil. In this work, amounts of CO2, CO, main hydrocarbon gases and PM2.5 emitted during deforestation fires, under real conditions directly in Brazilian Amazonia, were determined. A brief discussion of the relationship between the annual emission of CO2 equivalent (CO2,eq) and Paris Agreement was conducted. Experimental fires were carried out in Western Amazonia (Candeias do Jamari, Rio Branco and Cruzeiro do Sul) and results were compared with a previous fire carried out in Eastern Amazonia (Alta Floresta). The average total fresh biomass on the ground before burning and the total biomass consumption were estimated to be 591 ton ha−1 and 33%, respectively. CO2, CO, CH4, and non–methane hydrocarbon (NMHC) average emission factors, for the four sites, were 1568, 140, 8, and 3 g kg−1 of burned dry biomass, respectively. PM2.5 showed large variation among the sites (0.9–16 g kg−1). Emissions per hectare of forest were estimated as 216,696 kg of CO2, 18,979 kg of CO, 1,058 kg of CH4, and 496 kg of NMHC. The average annual emission of equivalent CO2 was estimated as 301 ± 53 Mt year−1 for the Brazilian Amazonia forest. From 2013, the estimated CO2,eq showed a trend to increase in Amazon region. The present study is an alert and provides important information that can be used in the development of the public policies to control emissions and deforestation in the Brazilian Amazonia.
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