Preparation of GO/MIL-101(Fe,Cu) composite and its adsorption mechanisms for phosphate in aqueous solution

Environmental Science and Pollution Research - In this study, MIL-101(Fe), MIL-101(Fe,Cu), and graphene oxide (GO)/MIL-101(Fe,Cu) were synthesized to compose a novel sorbent. The adsorption...     

Reduction of serum thyroxine concentrations by methylsulfonyl metabolites of tetra-, penta- and hexachlorinated biphenyls in male Sprague-Dawley rats

Male Sprague-Dawley rats received four consecutive intraperitoneal doses of nine methylsulfonyl (MeSO2) metabolites of tetra-, penta- and hexachlorinated biphenyls (tetra-, penta- and hexaCBs) to determine their effects on thyroid hormone levels. Nine MeSO2 metabolites, major MeSO2-PCBs detected in human milk, liver and adipose tissue, were 3-MeSO2-2,2',4',5-tetraCB (3-MeSO2-CB49), 3-MeSO2-2,3',4',5-tetraCB (3-MeSO2-CB70), 3-MeSO2-2,2',3',4',5-pentaCB (3-MeSO2-CB87), 3-MeSO2-2,2',4',5,5'-pentaCB (3-MeSO2-CB101), 4-MeSO2-2,2',4',5,5'-pentaCB (4-MeSO2-CB101), 3-MeSO2-2,2',3',4',5,6-hexaCB (3-MeSO2-CB132), 3-MeSO2-2,2',3',4',5,5'-hexaCB (3-MeSO2-CB141), 3-MeSO2-2,2',4',5,5',6-hexaCB (3-MeSO2-CB149) and 4-MeSO2-2,2',4',5,5',6-hexaCB (4-MeSO2-CB149). All nine MeSO2 metabolites (20 micromol/kg once daily for four days) reduced serum total thyroxine levels (16-44%) at a much lower dose than phenobarbital (431 micromol/kg once daily for four days) on days 2, 3, 4 and 7 after the last dosage. Total triiodothyronine level was reduced 37% by treatments with 3-MeSO2-CB49 and 3-MeSO2-CB149 at day 7, but increased 35% and 38% by 3-MeSO2-CB70 and 4-MeSO2-CB101 at days 3 and 4, respectively. The reductions in thyroxine levels led to an increase in thyroid-stimulating hormone levels by 3-MeSO2-CB49, 3-MeSO2-CB87, 3-MeSO2-CB101, 3-MeSO2-CB132, 3-MeSO2-CB141, 3-MeSO2-CB149 and 4-MeSO2-CB149. A 30% increase in thyroid weight was produced by 3-MeSO2-CB101 and 3-MeSO2-CB141 treatments. Total cytochrome P450 content and the activity of 7-pentoxyrosorufin O-dealkylase were increased by all seven 3-MeSO2-PCBs. 3-MeSO2-CB49, 3-MeSO2-CB87, 3-MeSO2-CB101 and 3-MeSO2-CB132 also increased the activity of 7-ethoxyresorufin O-dealkylase. Thus, it is likely that all nine tested MeSO2 metabolites could influence thyroid hormone metabolism. The results show that tested 3- and 4-MeSO2 metabolites of tetra-, penta- and hexaCBs reduce thyroid hormone levels in rats, suggesting that the metabolites may act as endocrine-disrupters.     

Adsorption and photocatalytic properties of porphyrin loaded MIL-101 (Cr) in methylene blue degradation

Environmental Science and Pollution Research - In this study for the very first time, zinc tetraphenylporphyrin (ZnTPP) was loaded into MIL-101 (Zn[TPP]@MIL-101) to perform an adsorptive and...     

Significance of Bacillus subtilis strain SJ-101 as a bioinoculant for concurrent plant growth promotion and nickel accumulation in Brassica juncea

In this study, a nickel (Ni)-tolerant Bacillus subtilis strain SJ-101 was characterized based on the 16SrDNA homology and phylogenetic analysis. The role of this strain ascertained in facilitating Ni accumulation in the Indian mustard plant (Brassica juncea [L]. Czern and Coss) var. Pusa Bold (DIR-50), to elucidate the potential of Ni phytoremediation in combination with metal-tolerant rhizobacteria. The data revealed that the plants exposed to NiCl2 (1750 mg kg(-1)) in soil bioaugmented with strain SJ-101 have accumulated 0.147% Ni vis-à-vis 0.094% accumulation in dry biomass of the plants grown in uninoculated soil. The strain SJ-101 has also exhibited the capability of producing indole acetic acid (IAA) (55 microg ml(-1)), and solubilizing inorganic phosphate (90 microg ml(-1)) in specific culture media. The pot culture experiments clearly demonstrated the beneficial effects of bioinoculant strain SJ-101 with significant increase (p<0.05) in the plant growth attributes in untreated control soil. Furthermore, the protective effect of the strain SJ-101 against Ni phytotoxicity was evident in plants grown in soil treated with NiCl2 in concentration range of 250-1750 mg kg(-1). Thus, it is suggested that the strain SJ-101 owing to its intrinsic abilities of plant growth promotion, and attenuation of soil Ni by biosorption and bioaccumulation, could be exploited for bacteria-assisted phytoaccumulation of this toxic heavy metal from contaminated sites.     

Methylsulfonyl PCB and DDE metabolites and their enantioselective gas chromatographic separation in human adipose tissues, seal blubber and pelican muscle

In the present investigation, eleven human adipose tissue samples, two seal blubber samples and two pelican muscles samples were analyzed with regard to their concentrations of PCB parent compounds as well as to the respective chiral methylsulfonyl metabolites 3-MeSO2-CB 91, 4-MeSO2-CB 91, 3-MeSO2-CB 95, 4-MeSO2-CB 95, 3-MeSO2-CB 149, 4-MeSO2-CB 149, 3-MeSO2-CB 132, 4-MeSO2-CB 132, 3-MeSO2-CB 174, and 4-MeSO2-CB 174 and the achiral metabolites 3-MeSO2-CB 49, 4-MeSO2-CB 49, 3-MeSO2-CB 101, 4-MeSO2-CB 101, 3-MeSO2-CB 110, 4-MeSO2-CB 110 and 3-MeSO2-DDE. In order to verify enantioselective transformation processes and to compare the different enzymatic transformation pathways in birds and mammals, the enantioselective excesses of the chiral PCB-metabolites were determined by enantioselective gas chromatography with electron capture and mass spectrometric detection using modified cyclodextrin phases, including heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/OV1701 (1:1) for the parent PCBs and heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/SE52 (1:4) for the metabolites, respectively.     

Contamination of human milk in Middle Hesse, Germany--a cross-sectional study on the changing levels of chlorinated pesticides, PCB congeners and recent levels of nitro musks

Human milk samples from women in Middle Hesse, Germany were chemically analyzed for contamination levels of alpha-, beta- and gamma-HCH, HCB, p,p'-DDE and p,p'-DDT as well as the PCB-congeners no. 28, 31, 49, 52, 101, 118, 138, 153, 156, 170 and 180. Changes in concentrations of these compounds in human milk over an extended time period were studied by comparing samples from 1984/85, 1990/91 and 1995. In addition, concentrations of the nitro-aromatic compounds musk xylene and musk ketone were determined in the 1995 samples. The study showed statistically highly significant (p<0.001) reductions in levels of beta- and gamma-HCH, HCB, p,p'-DDE and p,p'-DDT, in human milk from 1995 compared to samples from 1984/85. A weakly significant reduction (p<0.05) of alpha-HCH was also observed. For low-chlorinated PCB congeners, on the other hand, a highly significant increase of PCB no. 28 was detected and concentrations of congeners no. 31, 49 and 52 remained unchanged. Concentrations of the high-chlorinated congeners no. 101, 138, 153 and 180 dropped (highly significant). A highly significant reduction of PCB no. 118 and 156 occurred between 1990/91 and 1995, but a highly significant increase was found for no. 170. Lower levels of hydrocarbon contamination of human milk samples from 1995 than were found in samples from 1984/85 and 1990/91 can be seen to result partially from voluntary reductions, but primarily reflect restrictive environmental legislation in the Federal Republic of Germany. Mean concentrations of musk xylene and musk ketone in samples from 1995 were 41 microg/kg and 10 microg/kg milk fat, respectively.     

Analysis of 4-nonylphenols, phthalates, and polychlorinated biphenyls in soils and biosolids

When sewage sludge is added to agricultural land, organic chemicals contaminants are also added. The fate of these chemicals, particularly those shown to have oestrogenic potential, has received much research and regulatory interest in recent years. A method was developed for the analysis of 4-nonylphenols, phthalates, and PCB congeners in soils, mesophilic anaerobially digested dewatered (MADD) sewage sludge, and MADD sludge-amended soil. After Soxhlet-extraction, the 4-nonylphenols and phthalates were separated from the PCBs on an isolute cyanopropyl SPE cartridge and analysed by GC-MS directly. The PCBs were acid treated on a Bakerbond PCB-A cartridge, then passed through a gel filtration column of Biobeads SX-3 resin, before GC-MS analysis. The method was successfully validated and then used for routine analysis, where average recoveries of the surrogate standards were 83+/-17% (4-n-heptylphenol), 96+/-11% (dimethyl-tere-phthalate), 101+/-12% (dibenzyl-phthalate), and 79+/-13% (PCBs 6, 54, 104, 155, and 198).     

Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether

Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.     

Trends in organochlorine residue concentrations and burdens in grey seals (Halichoerus grypus) from Sable Is., NS, Canada, between 1974 and 1994

In blubber from maternal grey seals (Halichoerus grypus) from Sable Is., NS, sigma DDT (p,p'-DDE and p,p'-DDT) concentrations declined from 12 micrograms/g lipid in 1974 to 0.5 microgram/g in 1994. Pup blubber sigma DDT concentrations were about 60% of those of their mothers, and declined at similar rates. In maternal seals, p,p'-DDE increased from 56% sigma DDT in 1974 to 89% in 1994. Polychlorinated biphenyl concentrations did not change between 1976 and 1988, but then declined; the relative proportion of chlorobiphenyl (CB) 101 increased, and those of CBs 170 and 187 decreased between 1985 and 1991. Concentrations of alpha-hexachlorocyclohexane and trans-nonachlor declined after 1988, and of oxychlordane after 1992; concentrations of hexachlorobenzene were constant between 1984 and 1994.     

Sorption of PAHs and PCBs to activated carbon: coal versus biomass-based quality

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N₂ and CO₂ adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15 Å than the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources.     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.     

Effect of mono-ortho and di-ortho substituted polychlorinated biphenyl (PCB) congeners on leopard frog survival and sexual development

We tested the effect of mono-ortho and di-ortho PCB congeners on northern leopard frog (Rana pipiens) hatching success, survival and sexual development. Embryos and tadpoles were exposed to two levels (0.5 and 50 microg/l) of two PCBs. PCBs 101 and 70 were selected because they were present in amphibians collected in the Fox River-Green Bay ecosystem and they have the theoretical structural requirements to be able to bind to the estrogen receptor and mediate estrogenic responses. The exposure of leopard frog embryos and tadpoles to PCB 70 and 101 did not significantly affect hatchability, survival, deformities or growth. There were significant departures from the expected 50:50 sex ratio in tadpoles/froglets exposed to PCB 101 and PCB 70. In all the cases of significant departure, the bias was towards higher number of females. Decrease in the proportion of male gonads and increase in the proportion of intersex gonads were observed with increasing PCB tissue concentrations. The effects of PCB congeners on sexual differentiation occur at concentrations higher than observed in frogs in the Fox River/Green Bay ecosystem.     

Pesticide contamination profiles of water, sediment and aquatic organisms in the effluent of Gaobeidian wastewater treatment plant

Organochlorine pesticides (OCPs, including DDT, HCH and HCB) and six indicator polychlorinated biphenyls (PCB 28, 52, 101, 138, 153, and 180) were measured in water, sediment, zooplankton, fish and Chinese softshell turtle (Pelodiscus sinensis) from Gaobeidian Lake, which is located in the effluent of Gaobeidian wastewater treatment plant (WWTP) in Beijing, China. DDTs were dominant except for in water. In water, the concentrations of DDTs (6.22 ng l(-1)) and HCHs (18.0 ng l(-1)) were less than the limits (l000 ng l(-1) for DDTs and 5000 ng l(-1) for HCHs). However, PCBs concentration (20.8 ng l(-1)) exceeded the limit (14 ng l(-1)) suggested by the United States Environmental Protection Agency (USEPA). The high ratio of p,p'-DDT/DDTs (0.80) in water suggested that DDTs had recently been discharged into the ambient environment despite a longtime ban in China. For fish and Pelodiscus sinensis, the accumulation patterns of OCPs and PCBs were different in muscle and liver. And HCB and PCB 153 were significant different in different species (p<0.05). PCBs were dominated by PCB 52 in zooplankton, but by PCB 138 and 153 in Pelodiscus sinensis. The highest food web magnification factor (FWMF) was 4.83 for p,p'-DDT and the second highest was 4.36 for PCB 101 in Gaobeidian Lake. As compared with the other studies, biomagnification in the present study was not obvious. Trophic levels and age were two important factors that might contribute to the bioaccumulation in the present study.     

Sustainable adsorptive removal of antibiotics from aqueous streams using Fe3O4-functionalized MIL101(Fe) chitosan composite beads

Environmental Science and Pollution Research - In this study, we synthesized recyclable Fe3O4-functionalized MIL101(Fe) chitosan composite beads for the removal of tetracycline (TC), doxycycline...     

Polychlorinated biphenyl congener patterns in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed, western Massachusetts, USA, using a novel statistical approach

A novel application of a commonly used statistical approach was used to examine differences in polychlorinated biphenyl (PCB) congener patterns among locations and sample matrices in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed in western Massachusetts, USA. The most prevalent PCB congeners in tree swallow tissue samples from the Housatonic River watershed were Ballsmitter Zell numbers 153, 138, 180, 187, 149, 101, and 170. These congeners were seven of the eight most prevalent congeners in Aroclor 1260, the PCB mixture that was the primary source of contamination in the Housatonic River system. Using paired-Euclidean distances and tolerance limits, it was demonstrated that congener patterns in swallow tissues from sites on the main stem of the Housatonic River were more similar to one another than to two sites upstream of the contamination or from a nearby reference area. The congener patterns also differed between the reference area and the two upstream tributaries and between the two tributaries. These pattern differences were the same in both pipper (eggs or just hatched nestlings) and 12-day-old nestling samples. Lower-chlorinated congeners appeared to be metabolized in nestlings and pippers compared to diet, and metabolized more in pippers compared to nestlings. Euclidean distances and tolerance limits provide a simple and statistically valid method to compare PCB congener patterns among groups.     

An analysis between financial development,institutions, and the environment: a global view

Financial development is important for the growth of a country which indirectly affects the environment adversely through industrialization. However, in the presence of strong institutions, this adverse effect can be reduced. The main concern of the present study is to estimate the relation between CO₂ and financial development (FD) in the presence of economic institutions as an interactive term. A sample of 101 countries has been selected for econometric analysis for the period from 1995 to 2017. The cross-section dependence test statistics for dependency, CIPS and CADF for panel unit root test, Westerlund test to ascertain the long-run affiliations, and FMOLS to extract the long-run coefficients have been applied. Dumitrescu and Hurlin test is also employed to know about the causal nature of the panel series. The findings show that financial development has a positive relationship with CO₂. However, after inclusion of economic intuitions, the adverse impact of financial development on the environment is reduced. The study also confirms the presence of environmental Kuznets curve in the context of income and financial development. The findings imply that financial development can help to improve environment quality if it is accompanied with strong institutional framework such as assurance of property rights, government integrity, and liberalization in financial sector.

     

Polychlorinated biphenyls hot and cold seasons distribution in see water,sediment, and fish samples in the Khour-e-Mousa (Mah-Shahr), Iran

The concentrations of polychlorinated biphenyls (PCBs) were assessed at four sites in Khour-e-Mousa (Mah-Shahr), Iran. Sea water, sediment and fish (cynoglossus bilineatus) samples were taken at each site and were analysed for PCB levels. To investigate the possible source of PCBs found in fish samples, sediments and waters were collected from four sites (D1, D2, D3, and D4) and studied. The relationship between PCB concentrations in sediment, water and fish is discussed. The results indicate that PCBs are detected in all fish samples and its concentration range from 3.2 to 102.7 μg kg^?1 dry weight and 5.4–149.7 μg kg^?1 dry weight in cold and warm seasons, respectively. The D2 and D4 sites were found to have the highest and lowest levels of PCB concentrations, respectively. Total congener PCB (CB, 28, 52, 44, 101, 149, 118, 153, 138, and 180) concentrations at the sediment samples for D1, D2, D3, and D4 sites ranged from 1.6 to 30.9 μg kg^?1 dry weight and 2.3–47.1 μg kg^?1 dry weight in cold and warm seasons, respectively. The total PCB concentrations for D2 site were found to be significantly higher than other three sites. Total water congener PCB (CB, 28, 52, 44, 101, 149, 118, 153, 138, and 180) concentrations ranged from 0.01 to 0.25 μg L^?1 and 0.02–0.39 μg L^?1 in cold and warm seasons, respectively.     

Characterization of the Odor Properties of 101 Petrochemicals Using Sensory Methods

The absolute and recognition thresholds, odor index, quality, and hedonic tone of 101 petrochemical compounds have been determined using a trained panel and a laboratory method. The odor fountain method combines the features of accurate results, simplicity, reproducibility, and speed.     

A scheme for black carbon and sulphate aerosols tested in a hemispheric scale,Eulerian dispersion model

Production, transport and deposition of sulphate and black carbon (BC) are simulated separating aerosol modes by production mechanisms, thus facilitating calculation of aerosol physical properties. The scheme uses explicit sulphur chemistry with prescribed oxidants and aerosol transformation based on Brownian coagulation rates, and is implemented in a 3-D, hemispheric-scale transport model with off-line meteorology from ECMWF. The components are DMS, SO₂, sulphate and BC. Simulations are made for the year 1988. Predicted results for sulphate agree well with the measurements, except for considerable underestimations in the Arctic. In Europe SO₂ is slightly overestimated and sulphate is slightly underestimated in cold seasons, whilst trends are less clear in North America. Compared to many other models, we estimate a smaller effective oxidation rate for SO₂ due to reduced rates in cold clouds; a shorter turnover time for sulphate (3.7 d) due to a probably too large below-cloud scavenging ratio; and slightly smaller sulphate column burdens. Our BC results are similar to Liousse et al.’s (1996, J. Geophys. Res. 101, 19.411–19.432) except in USA, whilst the concentrations in remote areas and the turnover time (3.7 d) are considerably smaller than Cooke and Wilson’s (1996, J. Geophys. Res. 101, 190.395–19.409). Agreements with available measurements are quite close to large anthropogenic emissions (including USA), but they are considerably underestimated in Arctic winter. Transition from hydrophobic to hydrophilic BC due to coagulation is swift (6% h^-1). Sensitivity tests emphasize that sub-cloud scavenging coefficients rely on careful assumptions about size distributions, and that more research is needed on sulphate production in ice-clouds. Emphasis should also be put on production of sulphate and hydrophilic BC boundary-layer clouds; inclusion of hydrophobic accumulation mode BC and sub-grid transition to hydrophilic BC in emitting grid squares.     

PCB-blood levels in teachers, working in PCB-contaminated schools

In order to get more information about potential health hazards due to indoor air PCBs the present study investigated the PCB indoor concentration in schools as well as the blood levels of 6 PCB-indicator congeners in teachers from these schools. 151 teachers (78 male and 73 female; mean age 48 years) from 3 contaminated and 2 control schools participated in the study. Maximal indoor air values for total PCBs (6 PCB-indicator congeners times 5) in schools ranged from 1587 to 10655 ng/m3. Blood analyses indicated an increase in mean PCB 28 level from 0.036 (control group) to 0.098 microg/l in teachers from a school with heavy contamination of low chlorinated PCB. But there was no significant increase of PCB 138, 153 and 180 in blood above the normal background concentrations in any of the contaminated schools (mean values of all groups: PCB 138 = 0.66, 153 = 0.95, 180 = 0.70 microg/l blood). The results of blood analyses and additional toxicokinetic calculations suggested that inhalative PCB-uptake in the most contaminated schools caused a minor increase above mean background-PCB concentrations in blood. In conclusion, despite high PCB indoor air levels in schools, there was only a moderate increase in blood concentrations of teachers, mainly due to congeners with low chlorination (PCB 28 to PCB 101).