Ionic surfactants may impact removal efficiency of organic contaminants from aqueous solution, but research regarding the adsorption mechanisms on surfactant-modified carbon nanotubes (CNTs) was limited. In this study, three multi-walled and one single-walled CNTs were used as adsorbents to investigate the adsorption behavior and mechanisms of ciprofloxacin (CIP) on CNTs modified by ionic surfactants (cationic CTAB (Cetyltrimethylamnonium bromide) or anionic SDS (Sodium dodecyl sulfate)). More than 80% (82–88%) of the total removed CIP on CTAB-modified CNTs occurred within the first 6 h, much higher than that on SDS-modified CNTs (57–78%). Modeling adsorption kinetics demonstrated that CIP adsorption on surfactant-modified CNTs was controlled by multiple and faster processes, and both external mass transfer and intraparticle diffusion are limiting factors. Relative to SDS, CTAB was significantly (P < 0.001) concentration-dependent in suppressing CIP removal. Besides, the increase in 1/n values of Freundlich model with increasing CTAB concentration suggested that CTAB could be a stronger competitor for CIP adsorption. Hydrophobic interactions predominated zwitterionic CIP adsorption on all CNTs tested, while electrostatic interactions could help control ionizable CIP adsorption on surfactant-modified CNTs depending upon pH. CIP adsorption on modified SWCNTs significantly declined with increasing ionic strength from 1 mM to 100 mM relative to those multi-walled CNTs because the more favorable aggregation of SWCNTs reduced the CIP adsorption, irrespective of which surfactant was added. Significant desorption hysteresis of adsorbed CIP released by SDS and water was observed, but not by CTAB, by which 32.6–54.4% of adsorbed CIP were removed. For SDS-modified CNTs, the mean release ratio (RR) followed an order of MWCNTs (0.075) > MHCNTs (0.058) > SWCNTs (0.057) > MCCNTs (0.049), significantly (P < 0.001) lower than CTAB-CNTs (0.37–0.56). It can be predicted that the tested surfactants co-existing with CNTs depress removal efficiency of diverse contaminants similar to CIP in aqueous systems.

Studies of circulating levels in difference sex and age classes, and maternal transfer of bisphenol A, 4-tert-octylphenol and 4- nonylphenol in the Baltic grey seal were performed from 2014-2017. Blood was collected from long-term captive adult males, pregnant females and pups. Milk was collected from nursing females. The aim of this study was not only to determine the concentrations of phenol derivatives, i.e. bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP), but also to try to evaluate the transfer of these compounds to the next generation in the final stage of foetal life and in the first few weeks of life in juvenile marine mammals. The measurements were carried out using high performance liquid chromatography. The obtained data show that all phenol derivatives are present in the blood of males, females and pups (range <0.07–101 ng·cm⁻³) and in female milk (range <0.1–406.3 ng·cm⁻³). The main source of phenol derivatives in organisms is food exposure. Gender, age, or number of births were not observed to have a significant effect on changes in phenol derivative levels in seal blood within the breeding group. In the prenatal stage of life, a small amount of BPA and alkylphenols was passed on to the offspring through the placenta. In the blood of the offspring the concentration of these compounds exceeded the concentration in the mother's blood 1.5-fold. During nursing, females detoxified their systems. Level of phenol derivatives in the pups blood increased linearly with its increasing concentrations in the mother's milk. On the other hand, the seafood diet which started after the physiological fasting stage of the pup, stabilised the levels of phenol derivatives below 10 ng ∙ cm⁻³.

This study investigated selected steroidal and phenolic endocrine disrupting compounds (EDCs) in the surface water of the Bahe River (China) using gas chromatography mass spectrometry (GC-MS). Their effect on the wild sharpbelly Hemiculter leucisculus was investigated. The concentrations of 4-t-octylphenol, nonylphenol, bisphenol-A, estrone, 17 β-estradiol, 17 α-Ethinylestradiol, and estriol were up to 126.0, 634.8, 1573.1, 55.9, 23.9, 31.5, and 5.2 ng L⁻¹ in the surface water, and up to 26.4, 103.5, 146.9, 14.2, 9.3, 13.8, and 1.3 ng g⁻¹ in the fish muscle tissue, respectively. High estrogen equivalent levels and hazard quotients were found in the middle and lower reaches of the river, and the pollution in these regions caused enhanced growth conditions, inhibition of gonad growth, and suppression of spermatogenesis in H. leucisculus. The up-regulation of Vitellogenin mRNA expression in male fish, collected from relatively heavily EDCs contaminated areas, indicates a potential estrogenic effect. The differential expression profiles of genes related to steroidogenesis at all sampling sites suggests that these endpoints may play an important role for the pollution monitoring of estrogenic EDCs in the Bahe River.

The ubiquitous presence of microplastics (MPs) has been demonstrated in all environmental compartments in the recent years. They are detected in air, freshwater, soil, organisms and particularly in marine ecosystems. Since sediments are known to be the major sink of many organic and inorganic pollutants, the aim of this study was to develop and validate a fast and cheap methodology to assess the MP contamination in intertidal sediments from the Gulf of Biscay (Pays de la Loire region, France). Sediments were sampled at three locations (Pays de la Loire region, France) and during two seasons: October 2015 and March 2016. The analytical protocol involved MP extraction from dried sediments using milliQ water and a centrifugation technique. After a filtration step of supernatants, MPs were detected and directly identified on the membrane filters using μFTIR spectroscopy in reflection mode. For the first time, the number of replicates allowing to obtain a satisfying representativeness of the whole sampled sediment was also evaluated at 10 replicates of 25 g each. The average number of MPs in sediments was 67 (±76) MPs/kg dw (N = 60) with no significant difference between sites and seasons. Ten different compositions of MPs were defined by μFT-IR with a high proportion of polypropylene (PP) and polyethylene (PE), 38 and 24%, respectively. Among MPs, mainly fragments (84%) were observed with main size classes corresponding to [>100 μm] and [50–100 μm] but no particles > 1 mm could be found suggesting that mainly small microplastics (<1 mm) were subject to vertical transport.

Undisturbed outdoor lysimeters containing arable loamy sand soil were used to examine the influence of either heavy rain events (high frequency of high rain intensity), steady rain (continuous rainfall of low rain intensity), and natural rainfall on the transport and retention of surfactant-stabilized silver nanoparticles (AgNP). In addition, the AgNP–soil associations within the Ap horizon were analyzed by means of particle-size fractionation, asymmetrical flow field-flow fractionation coupled with UV/Vis-detection and inductively coupled plasma mass spectrometer (AF4-UV/Vis-ICP-MS), and transmission electron microscopy coupled to an energy-dispersive X-ray (TEM-EDX) analyzer. The results showed that AgNP breakthrough for all rain events was less than 0.1% of the total AgNP mass applied, highlighting that nearly all AgNP were retained in the soil. Heavy rain treatment and natural rainfall revealed enhanced AgNP transport within the Ap horizon, which was attributed to the high pore water flow velocities and to the mobilization of AgNP–soil colloid associations. Particle-size fractionation of the soil revealed that AgNP were present in each size fraction and therefore indicated strong associations between AgNP and soil. In particular, water-dispersible colloids (WDC) in the size range of 0.45–0.1 μm were found to exhibit high potential for AgNP attachment. The AF4-UV/Vis-ICP-MS and TEM-EDX analyses of the WDC fraction confirmed that AgNP were persistent in soil and associated to soil colloids (mainly composed of Al, Fe, Si, and organic matter). These results confirm the particularly important role of soil colloids in the retention and remobilization of AgNP in soil. Furthermore, AF4-UV/Vis-ICP-MS results indicated the presence of single, homo-aggregated, and small AgNP probably due to dissolution.

Phosphorus (P) limitation has been demonstrated for micro-polluted surface water denitrification treatment in previous study. In this paper, a lab-scale comparative study of autotrophic denitrification (ADN) and heterotrophic denitrification (HDN) in phosphorus-limited surface water was investigated, aiming to find out the optimal nitrogen/phosphorus (N/P) ratio and the mechanism of the effect of P limitation on ADN and HDN. Furthermore, the optimal denitrification process was applied to the West Lake denitrification project, aiming to improve the water quality of the West Lake from worse than grade V to grade IV (GB3838-2006). The lab-scale study showed that the lack of P indeed inhibited HDN more greatly than ADN. The optimal N/P ratio for ADN and HDN was 25 and a 0.15 mg PO43--P L−1 of microbial available phosphorus (MAP) was observed. P additions could greatly enhance the resistance of ADN and HDN to hydraulic loading shock. Besides, The P addition could effectively stimulate the HDN performance via enriching the heterotrophic denitrifiers and the denitrifying phosphate-accumulating organisms (DNPAOs). Additionally, HDN was more effective and cost-effective than ADN for treating P-limited surface water. The study of the full-scale HDBF (heterotrophic denitrification biofilter) indicated that the denitrification performance was periodically impacted by P limitation, particularly at low water temperatures.

Crumpled graphene oxide nanosheets have drawn large attentions due to its compressibility and self-avoiding stacking as flat graphene sheets trend to aggregate and restack. Up to now, most of the synthesis approaches were relied on external substrates, such as elastic substrates or ultrasonic atomizer, and the crumpled structures were obtained in a solid state directly. Here we report a facile method to produce crumpled dispersive nanosheets in solution through general base-washing treatment by taking advantage of the amphipathy of GO nanosheets. With the dissociation of oxygen-functional groups on nanosheets in alkaline environment, highly water-soluble oxidative debris (OD) would fall off from the nanosheets due to the increase of electrostatic repulsions, and resulted in the crumple of the flat sheets, while the covalent oxygen-functional groups on the nanosheets were reserved. As a result, the nanosheets remained dispersible in solution, and could be used directly for surface modifications. Pt nanoparticles could be directly deposited onto both sides of the sheets through common nucleation and growth from precursor ions process. Compared with flat graphene-based hybrid, the catalytic performance of crumpled-graphene-Pt (CG-Pt) is more excellent and attractive, and corresponding apparent kinetic rate constant (kₐₚₚ) of CG-Pt toward 4-nitrophenol reduction is enhanced by 2.7–4.6-fold. This study provides a new and facile way to fabricate crumpled nanosheets and demonstrates to be easy modified for various purpose.

The need of more food production, an increase in acidic deposition and the large capacity of paddy to emit greenhouse gases all coincide in several areas of China. Studying the effects of acid rain on the emission of greenhouse gases and the productivity of rice paddies are thus important, because these effects are currently unknown. We conducted a field experiment for two rice croppings (early and late paddies independent experiment) to determine the effects of simulated acid rain (control, normal rain, and treatments with rain at pH of 4.5, 3.5 and 2.5) on the fluxes of CO₂, CH₄ and N₂O and on rice productivity in subtropical China. Total CO₂ fluxes at pHs of 4.5, 3.5 and 2.5 were 10.3, 9.7 and 3.2% lower in the early paddy and 28.3, 14.8 and 6.8% lower in the late paddy, respectively, than the control. These differences from the control were significant for pH 3.5 and 4.5. Total CH₄ fluxes at pHs of 4.5, 3.5 and 2.5 were 50.4, 32.9 and 25.2% lower in the early paddy, respectively, than the control. pH had no significant effect on CH₄ flux in the late paddy or for total (early + late) emissions. N₂O flux was significantly higher at pH 2.5 than 3.5 and 4.5 but did not differ significantly from the flux in the control. Global-warming potentials (GWPs) were lower than the control at pH 3.5 and 4.5 but not 2.5, whereas rice yield was not appreciably affected by pH. Acid rain (between 3.5 and 4.5) may thus significantly affect greenhouse gases emissions by altering soil properties such as pH and nutrient pools, whereas highly acidic rain (pH 2.5) could increase GWPs (but not significantly), probably partially due to an increase in the production of plant litter.

Plants have the ability to adapt themselves under stressed conditions through reprogramming their growth and development. Understanding the mechanisms regulating overall growth of stressed plant is an important issue for plant and environmental biology research. Although the role of NO in modulating arsenic (As) toxicity is known, nitric oxide (NO) induced alteration in auxin and nutrient related transporters during As stress in rice is poorly understood. Experimental results showed that As exposure decreased gene expression level of polar auxin transporter (PIN proteins), and nutrient transporter related genes (AMT, NRT, NiR, PHT, KTP). The improved tolerance induced by As + NO combination is attributed to reduced As accumulation in rice seedlings, improved root architectural changes, overall growth of plant, chlorophyll, protein content, and accumulation of mineral nutrients by reducing the ROS generation. Further, enhanced transcript levels of PIN proteins and mineral nutrition related genes were also observed under As + NO treatment. Additional biochemical data revealed enhanced oxidative stress by increasing the level of antioxidant enzymes, and stress-related parameters. Overall, the study provides an integrated view of plant response during As + NO interaction to change the plant metabolism through different cellular processes.

To investigate the effect of arbuscular mycorrhizal fungi (AMF) on boron (B) toxicity in plants under the combined stresses of salt and drought, Puccinellia tenuiflora was grown in the soil with the inoculation of Funneliformis mosseae and Claroideoglomus etunicatum. After three weeks of treatment, the plants were harvested to determine mycorrhizal colonization rates, plant biomass, as well as tissue B, phosphorus, sodium, and potassium concentrations. The results show that the combined stresses reduced mycorrhizal colonization. Mycorrhizal inoculation significantly increased plant biomass while reduced shoot B concentrations. Mycorrhizal inoculation also slightly increased shoot phosphorus and potassium concentrations, and reduced shoot sodium concentrations. F. mosseae and C. etunicatum were able to alleviate the combined stresses of B, salt, and drought. The two fungal species and their combination showed no significant difference in the alleviation of B toxicity. It is inferred that AMF is able to alleviate B toxicity in P. tenuiflora by increasing biomass and reducing tissue B concentrations. The increase in plant phosphorus and potassium, as well as the decrease in sodium accumulation that induced by AMF, can help plant tolerate the combined stresses of salt and drought. Our findings suggest that F. mosseae and C. etunicatum are potential candidates for facilitating the phytoremediation of B-contaminated soils with salt and drought stress.