Enhanced degradation of trichloroethylene using bentonite-supported nanoscale Fe/Ni and humic acids

Nanoscale zero-valent iron, named nano-Fe⁰, is a reagent used to degrade trichloroethylene in groundwater. However, the efficiency of nano-Fe⁰ is moderate due to issues of dispersion and reactivity. As an alternative we synthesized bentonite-supported nanoscale Fe/Ni bimetals, named bentonite-Fe/Ni, to test the degradation of trichloroethylene in the presence of Suwannee River humic acids, as a representative of natural organic matter. 0.1 mmol/L trichloroethylene was reacted with 0.5 g/L of nano-Fe⁰, bentonite-Fe, Fe/Ni, and bentonite-Fe/Ni nanoparticles. Results show first that without humic acids the reaction rate constants k _obs were 0.0036/h for nano-Fe⁰, 0.0101/h for bentonite-Fe, 0.0984/h for Fe/Ni, and 0.181/h for bentonite-Fe/Ni. These findings show that bentonite-Fe/Ni is the most efficient reagent. Second, the addition of humic acids increased the rate constant from 0.178/h for 10 mg/L humic acids to 0.652/h for 40 mg/L humic acids, using the bentonite-Fe/Ni catalyst. This finding is explained by accelerated dechlorination by faster electron transfer induced by humic quinone moieties. Indeed, the use of 9, 10-anthraquinone-2, 6-disulfonate as a humic analogue gave similar results.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Antioxidant effect of lignite humic acids and its salts on the thermo-oxidative stability/degradation of polyvinyl alcohol blends

We demonstrate the antioxidant potential of humic acids in (green) polymer chemistry. Lignite humic acids and its sodium and ammonium salts were mixed at different concentrations with polyvinyl alcohol and thermogravimetry was used to assess the influence on the thermo-oxidative stability of resulted blends. Both protonized form and ammonium salt of humic acids caused increased stability of investigated polymers in the studied concentration range (0.5–10% of humic acids in polymer). In contrast to protonized form, the ammonium salt also showed moderating effect on polymer degradation kinetics. Sodium salts caused substantially lower stabilizing effect and presence of 10% of humic matter caused even destabilization. In all cases, however, when the degradation has already started, the presence of humic acids and its salts caused more intensive polymer decomposition, which resulted in lower weight of char.     

Development and application of “U.S.E.D.”: A hydroclimate lake stratification model

Two model types are currently in use to model the thermal stratification cycle in lakes and reservoirs: the eddy diffusion and the mixed layer (or integral energy) approaches. Here the former is analysed and developments are proposed to remove the empiricisms previously implicit in these models. These discussions permit the reformulation of K_H0 independently of current shear, together with an expression for R_i. The deduced formulae are in good agreement with observations. The newly formulated model (the University of Salford eddy diffusion model, U.S.E.D.) is subsequently used in simulations of lakes and reservoirs at different latitudes which are found to be in good agreement with observations without requiring inter-site calibration.     

Assessing effects of land use on landscape connectivity: loss and fragmentation of western U.S. forests

Effects of land-use change on the conservation of biodiversity have become a concern to conservation scientists and land managers, who have identified loss and fragmentation of natural areas as a high-priority issue. Despite urgent calls to inform national, regional, and state planning efforts, there remains a critical need to develop practical approaches to identify where important lands are for landscape connectivity (i.e., linkages), where land use constrains connectivity, and which linkages are most important to maintain network-wide connectivity extents. Our overall goal in this paper was to develop an approach that provides comprehensive, quantitative estimates of the effects of land-use change on landscape connectivity and illustrate its use on a broad, regional expanse of the western United States. We quantified loss of habitat and landscape connectivity for western forested systems due to land uses associated with residential development, roads, and highway traffic. We examined how these land-use changes likely increase the resistance to movement of forest species in non-forested land cover types and, therefore, reduce the connectivity among forested habitat patches. To do so, we applied a graph-theoretic approach that incorporates ecological aspects within a geographic representation of a network. We found that roughly one-quarter of the forested lands in the western United States were integral to a network of forested patches, though the lands outside of patches remain critical for habitat and overall connectivity. Using remotely sensed land cover data (ca. 2000), we found 1.7 million km2 of forested lands. We estimate that land uses associated with residential development, roads, and highway traffic have caused roughly a 4.5% loss in area (20 000 km2) of these forested patches, and continued expansion of residential land will likely reduce forested patches by another 1.2% by 2030. We also identify linkages among forest patches that are critical for landscape connectivity. Our approach can be readily modified to examine connectivity for other habitats/ecological systems and for other geographic areas, as well as to address more specific requirements for particular conservation planning applications.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

离体模型预测鱼体肝脏清除速率：鲑鱼肝细胞和肝脏S9组分的比较

将离体肝细胞和肝脏S9组分用于获取鱼类的体外生物转化数据可以优化模拟评估对化学物质的生物富集作用。然而涉及2种方式之间的直接对比的研究却几乎没有。本研究采用冷藏保存的鲑鱼肝细胞来测定对于6种多环芳烃(PAHs)的体外本征清除速率。我们运用测定结果推测体内本征清除速率,并将其作为输入值输入一种充分搅匀的肝脏模型中来预测肝清除速率。将事先由体外灌流肝脏测定的速率作为参考来评价预测结果。在2种竞争结合的假说前提下,由鲑鱼肝细胞测出的肝清除速率与实现的测定结果基本一致(6种多环芳烃中的5种都保持在2.1倍差异以下)。尽管多环芳烃的高代谢率是可能的原因之一,这些发现与之前由肝脏S9组分得出的结果相似。对苯并芘这一种化合物而言,由S9数据得出的体内本征清除速率是由肝细胞得出结果的10倍左右,这一结果可能是由细胞吸收速率造成的传播限制引起的。尽管苯并芘的结果差异较大,由任何一种体外测试方法得出的体内本征清除速率结果通常是一致的。这些结果显示离体肝细胞和肝脏S9组分2种系统均可用于优化鱼类的生物富集评估,尤其对于体外反应速率较高的情况。不同系统在化工领域的应用性是否相同则需要进一步的研究工作。
精选自Kellie A. Fay, Patrick N. Fitzsimmons, Alex D. Hoffman, John W. Nichols. Comparison of trout hepatocytes and liver S9 fractions as in vitro models for predicting hepatic clearance in fish. Environmental Toxicology and Chemistry: Volume 36, Issue 2, pages 463–471, July 2017. DOI: 10.1002/etc.3572
详情请见http://onlinelibrary.wiley.com/wol1/doi/10.1002/etc.3572/full
     

Stimulatory effect of ingested protein and/or free amino acids on the secretion of the gastro-endocrine hormone cholecystokinin and on tryptic activity, in early-feeding herring larvae, Clupea harengus

In the larvae of many marine teleosts, the stomach is absent until they approach or attain metamorphosis. Consequently, the formation of chyme containing specific free amino acids from the gastric digestion of protein, which are believed to be signals initiating the release of the digestive hormone cholecystokinin (CCK), is lacking. CCK, when secreted into the blood circulation from specialized intestinal cells, stimulates gallbladder motility and is a key factor causing the release of pancreatic digestive enzymes into the gut lumen. Using first-feeding Atlantic herring larvae (Clupea harengus) as a model, the aim of the present study was to determine if a CCK response together with tryptic activity could be elicited in larvae ingesting dietary protein and/or FAA. Larvae were tube fed single lamellar liposome vesicles (SLV) containing: (1) physiological saline (PS), (2) bovine serum albumin (BSA), (3) specific free amino acids (FAA), or (4) a ratio (1:1) of BSA and FAA. The CCK and trypsin levels were then assayed (radio-immunoassay) at 0, 15, 60 and 120 min after tube feeding. A marked CCK response was elicited in all treatments compared to the PS control at 15 and 30 min and was significant (p<0.05) at 120 min after tube feeding. Larvae tube fed the FAA treatment exhibited CCK levels that increased linearly from 1.6 to 5.6 fmol mg^-1 dry weight (DW) after 2 h of digestion, although this response was below the BSA and BSA:FAA treatments. The BSA and BSA:FAA treatments, after 15 min of digestion, showed a rapid CCK increase, over the PS and the FAA liposome treatments, to 8.1 and 5.4 fmol mg^-1 DW, respectively. At the end of the assay, BSA and BSA:FAA demonstrated similar levels (10.2 and 9.2 fmol mg^-1 DW, respectively). Larvae tube fed the PS control or the FAA liposome treatment did not demonstrate any appreciable increase in tryptic activity during the 2 h digestion period (0.03-0.071 and 0.03-0.048 mU mg^-1 DW, respectively). In contrast, the BSA:FAA treatment increased from 0.03-0.148 mU mg^-1 DW 1 h after feeding, which was significantly (p<0.05) higher than the PS and FAA liposomes, and then decreased markedly (0.085 mU mg^-1 DW) after 2 h of digestion. The larvae tube fed BSA liposomes, however, demonstrated steadily increasing tryptic activity throughout the sampling period, attaining 0.255 mU mg^-1 DW after 2 h, which was significantly (p<0.05) more than all the other treatments. The results showed that ingested liposomes containing FAA or the protein BSA or a combination of these two nutrients effectively stimulated CCK production in first-feeding herring larvae. In contrast, liposomes containing only physiological saline did not elicit a CCK response. In addition, liposomes containing BSA stimulated tryptic activity in herring larvae, which was not observed in fish fed liposomes that included only FAA or PS. This suggests that a suitable protein substrate is required to regulate protein digestion.     

三氯生对青海弧菌Q67和人乳腺癌细胞MCF-7的时间毒性

三氯生(triclosan,TCS)是一种广谱性抗菌剂,2005年欧盟水框架指令将TCS列为一种新型污染物。目前对TCS的研究局限于急性毒性实验,关于TCS毒性随时间的变化以及不同溶解状态下TCS的毒性差异的研究却鲜有报道。应用以96孔微板为暴露反应载体的微板毒性分析法,添加氢氧化钠(NaOH)或使用二甲亚砜(DMSO)作为助溶剂溶解TCS,分别测定其对青海弧菌Q67的相对发光抑制毒性(15min急性毒性和时间毒性)和对人乳腺癌细胞MCF-7在不同暴露时间(24、48和72h)内的细胞增殖抑制毒性。Q67的急性毒性实验结果表明,碱性条件下TCS的毒性(EC50=3.97(10-8mol.L-1)大于DMSO作为助溶剂时的毒性(EC50=1.68(10-4mol.L-1)。无论碱性条件还是DMSO助溶,TCS在不同暴露时间内对Q67的时间毒性没有明显差异。在不同暴露时间下MCF-7增殖抑制率实验中,DMSO作为助溶剂时,TCS的最高实验浓度为1.46(10-3mol.L-1,随着暴露时间的延长,抑制率在24、48和72h时分别为27.8%、44.2%和62.4%;碱性环境时TCS的最高实验浓度为1.39(10-6mol.L-1,随着暴露时间的延长,抑制率在24、48和72h时分别为20.2%、55.8%和73.9%。研究表明,在DMSO和NaOH作为助溶剂的条件下,TCS对MCF-7均存在时间毒性差异,并且NaOH碱性溶液中TCS对MCF-7的毒性远大于DMSO作为助溶剂时的毒性。     

Evaluation of fatty acids as biomarkers for a natural plankton community. A field study of a spring bloom and a post-bloom period off West Greenland

An investigation of the fatty acid composition of a natural arctic plankton community was carried out over two fishing banks located between 63°N and 65°N off the West Greenland coast. Samples for fatty acid analyses, species determination and biomass assessments of the plankton community were taken at the depth of fluorescence maximum. High biomass and diatom dominance during the spring bloom and low biomass and flagellate dominance in the post-bloom period were reflected by the fatty acid profiles. The total amount of fatty acid ranged from 55 to 132 µg l^-1 during the spring bloom and from 1 to 5 µg l^-1 during the post bloom. Analysis of the fatty acids showed that when the plankton was dominated by diatoms of the genera Thalassiosira and Chaetoceros, the proportions of C16:1(n-7) and C20:5(n-3) were correspondingly high. C18s, and particularly C18:1(n-9), were more abundant when the plankton was dominated by small autotrophic flagellates, primarily haptophytes. We found a good positive correlation between the common diatom marker, C16:1(n-7)/C16:0, and the biomass percentage of diatoms (r=0.742, P<0.001), as well as between the biomass percentage of flagellates and total C18 fatty acids (r=0.739, P<0.001). This supports the use of these specific fatty acids and fatty acid ratios as general biomarkers of the plankton community. However, the fatty acids are not specific enough to sufficiently characterise the composition of the plankton community, and microscopical support is needed to verify observed trends.     

COLIWAVE a simulation model for survival of E. coli O157:H7 in dairy manure and manure-amended soil

A simulation model was developed to investigate the relative effects of temperature, oxygen concentration, substrate content and competition by autochthonous microbial community on the oscillatory behaviour and survival of Escherichia coli O157:H7 in manure and manure-amended soil. The overall decline in E. coli O157:H7 was primarily determined by competition with autochthonous copiotrophic bacteria simulated by an inter-specific competition term according to Lotka-Volterra. Oscillations of bacterial populations were attained by the relationships between relative growth and death rates with readily available substrate content. The model contains a logistic and exponential relation of relative growth and death rates, respectively, of E. coli O157:H7 and copiotrophic bacteria with temperature, resulting in optimum curves for net growth rates similar to the curves reported in the literature. The model has been both calibrated and validated on experimental data. The model was used to perform sensitivity analysis and to evaluate different manure and soil management scenarios in terms of survival of E. coli O157:H7. The relative effects of changes in temperature on simulated survival time of E. coli O157:H7 were more pronounced than changes in oxygen condition. Testing manure storage scenarios with realistic data revealed that manure stored in a heap that was turned every week resulted in almost 70% reduction of E. coli O157:H7 survival compared to unturned manure. At the surface of a heap with unturned manure, simulated survival time was the longest (2.4 times longer than inside the same heap). The simulation model provides a new approach to investigating dynamic changes of invasive microorganisms in natural substrates such as manure or manure-amended soil.     

Seaweed secondary metabolites as antifoulants: effects of Dictyota spp. diterpenes on survivorship, settlement, and development of marine invertebrate larvae

Summary. A recent investigation showed that the brown seaweed Dictyota menstrualis was unfouled relative to co-occurring seaweeds, and that larvae of fouling invertebrates avoided settling on D. menstrualis due to chemicals on its surface. The secondary metabolites dictyol E and pachydictyol A are among the compounds found on this alga's surface. In the present study, we tested the effects of specific diterpenes from Dictyota on the survivorship, growth, and development of invertebrate larvae and developing juveniles that could foul seaweeds. Exposure to dictyol E, dictyol B acetate, pachydictyol A, and dictyodial from Dictyota menstrualis and D. ciliolata caused significant larval mortality, abnormal development, and reduce growth rates for three species of co-occurring invertebrates when their larvae were forced into contact with these metabolites. Larvae were damaged at metabolite concentrations as low as 5% of maximum possible surface concentrations of these compounds for the populations of Dictyota we studied. The negative effects of these secondary metabolites on potential foulers, in conjunction with data demonstrating larval avoidance of dictyol-covered surfaces, suggest that these compounds could function as chemical defenses against fouling, and could select for larvae that avoid hosts producing these metabolites. Received 25 May 1998; accepted 22 June 1998.     

Lipids and fatty acids as indicators of egg condition,larval feeding and maternal effects in Cape hakes (<Emphasis Type="Italic">Merluccius paradoxus</Emphasis> and <Emphasis Type="Italic">M. capensis</Emphasis>)

Cape hakes, Merluccius paradoxus and M. capensis, are important gadoid fish that are commercially harvested in the Benguela Current system off Namibia and South Africa. The aim of this study was to elucidate the nutritional condition and feeding preferences of their larvae. Hake eggs and larvae were sampled in austral spring of two consecutive years, 2007 and 2008, off the west coast of South Africa. They were identified to species using genetics, and total lipid content and fatty acid (FA) composition were analysed for each individual egg and larva to compare the condition of different early life stages of both hake species. Higher abundances of M. paradoxus eggs and larvae were consistently found compared to M. capensis. In both species, eggs contained wax esters (WE) and had significantly higher lipid content per dry mass than larvae. Lipid content as well as FA composition changed with the developmental stage of larvae. Quantities of essential fatty acid (EFA) increased with feeding of larvae due to dietary lipid incorporation. In 2007, yolk-sac larvae contained significantly lower total lipids than in 2008. It is argued that this was due to reduced lipid transfer by the spawning females to the eggs. These findings indicate that maternal effects are important in determining condition of hake larvae and that this may have an effect on their survival and subsequent recruitment.     

Differences in somatic and gonadic growth of sea urchins ( Stronglyocentrotus droebachiensis ) fed kelp ( Laminaria longicruris ) or the invasive alga Codium fragile ssp. tomentosoides are related to energy acquisition

The rocky subtidal community off the Atlantic coast of Nova Scotia has historically undergone a cyclical transition between Laminaria-dominated kelp beds and sea urchin-dominated barrens. Since the introduction of the invasive alga Codium fragile ssp. tomentosoides, a third community state has emerged: Codium-dominated algal beds. We conducted a 42-week feeding experiment in the laboratory, which mimicked the quantity and quality of food available to urchins (Strongylocentrotus droebachiensis) in each of these community states. Feeding rate, growth, reproduction, and survival of urchins fed either Laminaria longicruris or C. fragile ad libidum, or L. longicruris 2 days per month, were measured. Although the ad libidum feeding rate on C. fragile was higher than that on kelp, energy intake was lower. Urchins in the ad libidum kelp treatment were larger and had larger gonads than those in the C. fragile treatment. Urchins fed kelp infrequently exhibited little somatic and gonadic growth over the course of the experiment. Regression analysis revealed that urchin performance on these diets was strongly related to energy intake. Diet treatment had no effect on survival or gonad maturation. Although urchins can consume substantial amounts of C. fragile, it appears that they cannot, or do not, feed quickly enough to compensate for its lower nutritional value. Our results suggest that, although urchins feeding on C. fragile are capable of surviving, growing, and reproducing, the replacement of kelp by C. fragile in some areas might negatively affect urchin populations as they continue to repopulate the shallow subtidal zone.