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Assessing the remobilization of Antimony in sediments by DGT: A case study in a tributary of the Three Gorges Reservoir Full text
2016
Gao, Li | Gao, Bo | Zhou, Huaidong | Xu, Dongyu | Wang, Qiwen | Yin, Shuhua
The Three Gorges Reservoir (TGR) is one of the world's largest man-made hydropower projects, which has posed great challenges to the aquatic environment of the Yangtze River since the impoundment of water. As a non-essential toxic metalloid, information on the bioavailability of Antimony (Sb) in TGR sediments is lacking. Four sediment cores were collected from a tributary and the mainstream in the TGR to investigate the distribution and remobilization of Sb using the diffusive gradients in thin films (DGT) technique. The results showed that the concentrations of Sb obtained by DGT (CDGT-Sb) at all of the sampling stations were low (below 0.30 μg/L), compared to the relatively high Sb concentrations in the sediments. The lateral and vertical distributions of CDGT-Sb revealed different tendencies in overlying water and sediments at all of the sampling sites in the TGR, which may be attributed to anthropogenic impacts, the heterogeneity of sediments and the unevenness of the sediment-water interface (SWI) during the deployment of DGT probes. In addition, CDGT-Sb in the surface sediments were lower than those in the overlying water, and concentration gradients were found near the SWI, demonstrating that Sb has the potential to diffuse from the overlying water into the sediment. In the sediment cores, different peaks were discovered in the DGT probes and the remobilization of Sb simultaneously appeared in the vicinity of −10 cm. Correlation analysis showed that CDGT-Sb had no or negative correlation with CDGT-Fe and CDGT-Mn in all of the DGT probes, suggesting that the release of Sb was unassociated with Fe and Mn in the sediments in the study area.
Show more [+] Less [-]Enhanced dehydrochlorination of 1,1,2,2-tetrachloroethane by graphene-based nanomaterials Full text
2016
Li, Xuguang | Chen, Weifeng | Zhang, Chengdong | Li, Yao | Wang, Fanfan | Chen, Wei
Graphene oxide (GO) and reduced graphene oxide (RGO) materials contain a variety of surface O-functional groups that are chemically reactive. When released into the environment these materials may significantly affect the abiotic transformation of organic contaminants, and therefore, may alter their fate and risks. We found that two GO and five RGO materials that varied in C/O ratio, hydrophobicity, and type/distribution of surface O-functionality all had catalytic effects on the dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA). Even though the catalytic effects of the materials originated from their deprotonated surface O-functional groups, which served as conjugated bases to catalyze the reaction, the catalytic efficiencies of the materials did not correlate strongly with their surface O contents. The spectroscopic evidence (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy), surface charge data, and adsorption experiments demonstrated that the catalytic efficiencies of the GO/RGO materials were controlled by a complex interplay of the type and distribution of surface O-functionality, as well as adsorption affinity of the materials. Both Ca2+ and Mg2+ inhibited the catalytic efficiency of the materials by binding to the surface O-functional groups, and consequently, decreasing the basicity of the functional groups. At an environmentally relevant concentration of 10 mg/L, Suwannee River humic acid (used as a model dissolved organic matter) alone had little effect on the dehydrochlorination of TeCA. However, it could inhibit the catalytic efficiency of the GO/RGO materials by coating on their surface and thus, decreasing the adsorption affinity of these materials for TeCA. The findings further underline the potentially important impacts of nanomaterials on contaminant fate and effects in the environment.
Show more [+] Less [-]Degradation of cyclophosphamide and 5-fluorouracil by UV and simulated sunlight treatments: Assessment of the enhancement of the biodegradability and toxicity Full text
2016
Lutterbeck, Carlos Alexandre | Wilde, Marcelo Luís | Baginska, Ewelina | Leder, Christoph | Machado, Ênio Leandro | Kümmerer, Klaus
The presence of pharmaceuticals in the environment has triggered concern among the general population and received considerable attention from the scientific community in recent years. However, only a few publications have focused on anticancer drugs, a class of pharmaceuticals that can exhibit cytotoxic, genotoxic, mutagenic, carcinogenic and teratogenic effects. The present study investigated the photodegradation, biodegradation, bacterial toxicity, mutagenicity and genotoxicity of cyclophosphamide (CP) and 5-fluorouracil (5-FU). The photodegradation experiments were performed at a neutral to slight pH range (7–7.8) using two different lamps (medium-pressure mercury lamp and a xenon lamp). The primary elimination of the parent compounds was monitored by means of liquid chromatography tandem mass spectrometry (LC-IT-MS/MS). NPOC (non-purgeable organic carbon) analyses were carried out in order to assess mineralization rates. The Closed Bottle Test (CBT) was used to assess ready biodegradability. A new method using Vibrio fischeri was adopted to evaluate toxicity. CP was not degraded by any lamp, whereas 5-FU was completely eliminated by irradiation with the mercury lamp but only partially by the Xe lamp. No mineralization was observed for the experiments performed with the Xe lamp, and a NPOC removal of only 18% was registered for 5-FU after 256 min using the UV lamp. Not one of the parent compounds was readily biodegradable in the CBT. Photo transformation products (PTPs) resulting from photolysis were neither better biodegradable nor less toxic than the parent compound 5-FU. In contrast, the results of the tests carried out with the UV lamp indicated that more biodegradable and non-toxic PTPs of 5-FU were generated. Three PTPs were formed during the photodegradation experiments and were identified. The results of the in silico QSAR predictions showed positive mutagenic and genotoxic alerts for 5-FU, whereas only one of the formed PTPs presented positive alerts for the genotoxicity endpoint.
Show more [+] Less [-]Occurrence and persistence of antibiotic resistance genes in river biofilms after wastewater inputs in small rivers Full text
2016
Proia, Lorenzo | von Schiller, Daniel | Sànchez-Melsió, Alexandre | Sabater, Sergi | Borrego, Carles M. | Rodríguez-Mozaz, Sara | Balcázar, José Luis
The extensive use of antibiotics in human and veterinary medicine and their subsequent release into the environment may have direct consequences for autochthonous bacterial communities, especially in freshwater ecosystems. In small streams and rivers, local inputs of wastewater treatment plants (WWTPs) may become important sources of organic matter, nutrients and emerging pollutants, such as antibiotic resistance genes (ARGs). In this study, we evaluated the effect of WWTP effluents as a source of ARGs in river biofilms. The prevalence of genes conferring resistance to main antibiotic families, such as beta-lactams (blaCTX-M), fluoroquinolones (qnrS), sulfonamides (sul I), and macrolides (ermB), was determined using quantitative PCR (qPCR) in biofilm samples collected upstream and downstream WWTPs discharge points in four low-order streams. Our results showed that the WWTP effluents strongly modified the hydrology, physico-chemistry and biological characteristics of the receiving streams and favoured the persistence and spread of antibiotic resistance in microbial benthic communities. It was also shown that the magnitude of effects depended on the relative contribution of each WWTP to the receiving system. Specifically, low concentrations of ARGs were detected at sites located upstream of the WWTPs, while a significant increase of their concentrations was observed in biofilms collected downstream of the WWTP discharge points (particularly ermB and sul I genes). These findings suggest that WWTP discharges may favour the increase and spread of antibiotic resistance among streambed biofilms. The present study also showed that the presence of ARGs in biofilms was noticeable far downstream of the WWTP discharge (up to 1 km). It is therefore reasonable to assume that biofilms may represent an ideal setting for the acquisition and spread of antibiotic resistance determinants and thus be considered suitable biological indicators of anthropogenic pollution by active pharmaceutical compounds.
Show more [+] Less [-]Deep challenges for China's war on water pollution Full text
2016
Han, Dongmei | Currell, Matthew J. | Cao, Guoliang
China's Central government has released an ambitious plan to tackle the nation's water pollution crisis. However, this is inhibited by a lack of data, particularly for groundwater. We compiled and analyzed water quality classification data from publicly available government sources, further revealing the scale and extent of the crisis. We also compiled nitrate data in shallow and deep groundwater from a range of literature sources, covering 52 of China's groundwater systems; the most comprehensive national-scale assessment yet. Nitrate pollution at levels exceeding the US EPA's maximum contaminant level (10 mg/L NO3N) occurs at the 90th percentile in 25 of 36 shallow aquifers and 10 out of 37 deep or karst aquifers. Isotopic compositions of groundwater nitrate (δ15N and δ18ONO3 values ranging from −14.9‰ to 35.5‰ and −8.1‰ to 51.0‰, respectively) indicate many nitrate sources including soil nitrogen, agricultural fertilizers, untreated wastewater and/or manure, and locally show evidence of de-nitrification. From these data, it is clear that contaminated groundwater is ubiquitous in deep aquifers as well as shallow groundwater (and surface water). Deep aquifers contain water recharged tens of thousands of years before present, long before widespread anthropogenic nitrate contamination. This groundwater has therefore likely been contaminated due to rapid bypass flow along wells or other conduits. Addressing the issue of well condition is urgently needed to stop further pollution of China's deep aquifers, which are some of China's most important drinking water sources. China's new 10-point Water Pollution Plan addresses previous shortcomings, however, control and remediation of deep groundwater pollution will take decades of sustained effort.
Show more [+] Less [-]Sensitivity of the early-life stages of freshwater mollusks to neonicotinoid and butenolide insecticides Full text
2016
Prosser, R.S. | de Solla, S.R. | Holman, E.A.M. | Osborne, R. | Robinson, S.A. | Bartlett, A.J. | Maisonneuve, F.J. | Gillis, P.L.
Neonicotinoid insecticides can be transported from agricultural fields, where they are used as foliar sprays or seed treatments, to surface waters by surface or sub-surface runoff. Few studies have investigated the toxicity of neonicotinoid or the related butenolide insecticides to freshwater mollusk species. The current study examined the effect of neonicotinoid and butenolide exposures to the early-life stages of the ramshorn snail, Planorbella pilsbryi, and the wavy-rayed lampmussel, Lampsilis fasciola. Juvenile P. pilsbryi were exposed to imidacloprid, clothianidin, or thiamethoxam for 7 or 28 d and mortality, growth, and biomass production were measured. The viability of larval (glochidia) L. fasciola was monitored during a 48 h exposure to six neonicotinoids (imidacloprid, thiamethoxam, clothianidin, acetamiprid, thiacloprid, or dinotefuran), or a butenolide (flupyradifurone). The 7-d LC50s of P. pilsbryi for imidacloprid, clothianidin, and thiamethoxam were ≥4000 μg/L and the 28-d LC50s were ≥182 μg/L. Growth and biomass production were considerably more sensitive endpoints than mortality with EC50s ranging from 33.2 to 122.0 μg/L. The 48-h LC50s for the viability of glochidia were ≥456 μg/L for all seven insecticides tested. Our data indicate that neonicotinoid and butenolide insecticides pose less of a hazard with respect to mortality of the two species of mollusk compared to the potential hazard to other non-target aquatic insects.
Show more [+] Less [-]Soil microbial response to photo-degraded C60 fullerenes Full text
2016
Berry, Timothy D. | Clavijo, Andrea P. | Zhao, Yingcan | Jafvert, Chad T. | Turco, Ronald F. | Filley, Timothy R.
Recent studies indicate that while unfunctionalized carbon nanomaterials (CNMs) exhibit very low decomposition rates in soils, even minor surface functionalization (e.g., as a result of photochemical weathering) may accelerate microbial decay. We present results from a C60 fullerene-soil incubation study designed to investigate the potential links between photochemical and microbial degradation of photo-irradiated C60. Irradiating aqueous ¹³C-labeled C60 with solar-wavelength light resulted in a complex mixture of intermediate products with decreased aromaticity. Although addition of irradiated C60 to soil microcosms had little effect on net soil respiration, excess ¹³C in the respired CO2 demonstrates that photo-irradiating C60 enhanced its degradation in soil, with ∼0.78% of 60 day photo-irradiated C60 mineralized. Community analysis by DGGE found that soil microbial community structure was altered and depended on the photo-treatment duration. These findings demonstrate how abiotic and biotic transformation processes can couple to influence degradation of CNMs in the natural environment.
Show more [+] Less [-]Can field portable X-ray fluorescence (pXRF) produce high quality data for application in environmental contamination research? Full text
2016
Rouillon, Marek | Taylor, Mark P.
This research evaluates the analytical capabilities of a field portable X-ray fluorescence spectrometer (pXRF) for the measurement of contaminated soil samples using a matrix-matched calibration. The calibrated pXRF generated exceptional data quality from the measurement of ten soil reference materials. Elemental recoveries improved for all 11 elements post-calibration with reduced measurement variation and detection limits in most cases. Measurement repeatability of reference values ranged between 0.2 and 10% relative standard deviation, while the majority (82%) of reference recoveries were between 90 and 110%. Definitive data quality, the highest of the US EPA's three level quality ranking, was achieved for 15 of 19 elemental datasets. Measurement comparability against inductively coupled plasma atomic emission spectrometry (ICP-AES) values was excellent for most elements (e.g, r2 0.999 for Mn and Pb, r2 > 0.995 for Cu, Zn and Cd). Parallel measurement of reference materials revealed ICP-AES and ICP-MS measured Ti and Cr poorly when compared to pXRF. Individual recoveries of soil reference materials by both ICP-AES and pXRF showed that pXRF was equivalent to or better than ICP-AES values for all but two elements (Ni, As). This study demonstrates pXRF as a suitable alternative to ICP-AES analysis in the measurement of Ti, Cr, Mn, Fe, Cu, Zn, Sr, Cd, and Pb in metal-contaminated soils. Where funds are limited, pXRF provides a low-cost, high quality solution to increasing sample density for a more complete geochemical investigation.
Show more [+] Less [-]The Kuril Islands as a potential region for aquaculture: Trace elements in chum salmon Full text
2016
Khristoforova, Nadezhda K. | Tsygankov, Vasiliy Yu | Lukyanova, Olga N. | Boyarova, Margarita D.
The Kuril Islands region is considered promising for development of salmon aquaculture. There are 41 salmon fish hatcheries in the Sakhalin Island and the Kuril Islands, 34 of them are hatcheries of the chum. Therefore, concentrations of six elements (Zn, Cu, Cd, Pb, As, and Hg) were determined in chum salmon were caught in this region. The contents of toxic elements (Cd, Pb, As, and Hg) don't exceed their maximum permissible concentrations (MPC) according to the Russian sanitary standards, but concentration of Pb are closely to MPC. Increased concentrations of Pb in wild chum have the natural origin. The unusual conditions of the Western Pacific are formed under the influence such factors as volcanism and upwelling.
Show more [+] Less [-]Influence of fulvic acid on the colloidal stability and reactivity of nanoscale zero-valent iron Full text
2016
Dong, Haoran | Ahmad, Kito | Zeng, Guangming | Li, Zhongwu | Chen, Guiqiu | He, Qi | Xie, Yankai | Wu, Yanan | Zhao, Feng | Zeng, Yalan
This study investigated the effect of fulvic acid (FA) on the colloidal stability and reactivity of nano zero-valent iron (nZVI) at pH 5, 7 and 9. The sedimentation behavior of nZVI differed at different pH. A biphasic model was used to describe the two time-dependent settling processes (i.e., a rapid settling followed by a slower settling) and the settling rates were calculated. Generally, the settling of nZVI was more significant at the point of zero charge (pHpzc), which could be varied in the presence of FA due to the adsorption of FA on the nZVI surface. More FA was adsorbed on the nZVI surface at pH 5–7 than pH 9, resulting in the varying sedimentation behavior of nZVI via influencing the electrostatic repulsion among particles. Moreover, it was found that there was a tradeoff between the stabilization and the reactivity of nZVI as affected by the presence of FA. When FA concentration was at a low level, the adsorption of FA on the nZVI surface could enhance the particle stabilization, and thus facilitating the Cr(VI) reduction by providing more available surface sites. However, when the FA concentrations were too high to occupy the active surface sites of nZVI, the Cr(VI) reduction could be decreased even though the FA enhanced the dispersion of nZVI particles. At pH 9, the FA improved the Cr(VI) reduction by nZVI. Given the adsorption of FA on the nZVI surface was insignificant and its effect on the settling behavior of nZVI particles was minimal, it was proposed that the FA formed soluble complexes with the produced Fe(III)/Cr(III) ions, and thus reducing the degree of passivation on the nZVI surface and facilitating the Cr(VI) reduction.
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