All-Cellulose Composite Fibers Obtained by Electrospinning Dispersions of Cellulose Acetate and Cellulose Nanocrystals

All-cellulose composite fibers were produced by electrospinning dispersions containing cellulose acetate (CA) and cellulose nanocrystals (CNCs). Precursor polymer matrices were obtained after dispersion of CA with different degrees of substitution in a binary mixture of organic solvents. The obtained fibers of CA loaded with CNCs had typical widths in the nano- and micro-scale and presented a glass transition temperature of 145?°C. The CA component was converted to cellulose by using alkaline hydrolysis to yield all-cellulose composite fibers that preserved the original morphology of the precursor system. Together with Fourier Transform Infrared Spectroscopy fingerprints the thermal behavior of the all-cellulose composite fibers indicated complete conversion of cellulose acetate to regenerated cellulose. Noticeable changes in the thermal, surface and chemical properties were observed upon deacetylation. Not only the thermal transitions of cellulose acetate disappeared but the initial water contact angle of the web was reduced drastically. Overall, we propose a simple method to produce all-cellulose composite fibers which are expected to display improved thermo-mechanical properties while keeping the unique features of the cellulose polymer.     

A compilation of field surveys on gaseous elemental mercury (GEM) from contrasting environmental settings in Europe,South America,South Africa and China: separating fads from facts

Mercury is transported globally in the atmosphere mostly in gaseous elemental form (GEM, \( {\text{Hg}}_{\text{gas}}^{0} \) ), but still few worldwide studies taking into account different and contrasted environmental settings are available in a single publication. This work presents and discusses data from Argentina, Bolivia, Bosnia and Herzegovina, Brazil, Chile, China, Croatia, Finland, Italy, Russia, South Africa, Spain, Slovenia and Venezuela. We classified the information in four groups: (1) mining districts where this contaminant poses or has posed a risk for human populations and/or ecosystems; (2) cities, where the concentration of atmospheric mercury could be higher than normal due to the burning of fossil fuels and industrial activities; (3) areas with natural emissions from volcanoes; and (4) pristine areas where no anthropogenic influence was apparent. All the surveys were performed using portable LUMEX RA-915 series atomic absorption spectrometers. The results for cities fall within a low GEM concentration range that rarely exceeds 30 ng m^?3, that is, 6.6 times lower than the restrictive ATSDR threshold (200 ng m^?3) for chronic exposure to this pollutant. We also observed this behavior in the former mercury mining districts, where few data were above 200 ng m^?3. We noted that high concentrations of GEM are localized phenomena that fade away in short distances. However, this does not imply that they do not pose a risk for those working in close proximity to the source. This is the case of the artisanal gold miners that heat the Au–Hg amalgam to vaporize mercury. In this respect, while GEM can be truly regarded as a hazard, because of possible physical–chemical transformations into other species, it is only under these localized conditions, implying exposure to high GEM concentrations, which it becomes a direct risk for humans.     

Long-distance transport of Hg, Sb, and As from a mined area, conversion of Hg to methyl-Hg, and uptake of Hg by fish on the Tiber River basin, west-central Italy

Stream sediment, stream water, and fish were collected from a broad region to evaluate downstream transport and dispersion of mercury (Hg) from inactive mines in the Monte Amiata Hg District (MAMD), Tuscany, Italy. Stream sediment samples ranged in Hg concentration from 20 to 1,900 ng/g, and only 5 of the 17 collected samples exceeded the probable effect concentration for Hg of 1,060 ng/g, above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in Tiber River sediment varied from 0.12 to 0.52 ng/g, and although there is no established guideline for sediment methyl-Hg, these concentrations exceeded methyl-Hg in a regional baseline site (<0.02 ng/g). Concentrations of Hg in stream water varied from 1.2 to 320 ng/L, all of which were below the 1,000 ng/L Italian drinking water Hg guideline and the 770 ng/L U.S. Environmental Protection Agency (USEPA) guideline recommended to protect against chronic effects to aquatic wildlife. Methyl-Hg concentrations in stream water varied from <0.02 to 0.53 ng/L and were generally elevated compared to the baseline site (<0.02 ng/L). All stream water samples contained concentrations of As (<1.0–6.2 μg/L) and Sb (<0.20–0.37 μg/L) below international drinking water guidelines to protect human health (10 μg/L for As and 20 μg/L for Sb) and for protection against chronic effects to aquatic wildlife (150 μg/L for As and 5.6 μg/L for Sb). Concentrations of Hg in freshwater fish muscle ranged from 0.052–0.56 μg/g (wet weight), mean of 0.17 μg/g, but only 17 % (9 of 54) exceeded the 0.30 μg/g (wet weight) USEPA fish muscle guideline recommended to protect human health. Concentrations of Hg in freshwater fish in this region generally decreased with increasing distance from the MAMD, where fish with the highest Hg concentrations were collected more proximal to the MAMD, whereas all fish collected most distal from Hg mines contained Hg below the 0.30 μg/g fish muscle guideline. Data in this study indicate some conversion of inorganic Hg to methyl-Hg and uptake of Hg in fish on the Paglia River, but less methylation of Hg and Hg uptake by freshwater fish in the larger Tiber River.     

Allee effect limits colonization success of sexually reproducing zooplankton

Understanding the dynamics of populations at low density and the role of Allee effects is a priority due to concern about the decline of rare species and interest in colonization/invasion dynamics. Despite well-developed theory and observational support, experimental examinations of the Allee effect in natural systems are rare, partly because of logistical difficulties associated with experiments at low population density. We took advantage of fish introduction and removal in alpine lakes to experimentally test for the Allee effect at the whole-ecosystem scale. The large copepod Hesperodiaptomus shoshone is often extirpated from the water column by fish and sometimes fails to recover following fish disappearance, despite the presence of a long-lived egg bank. Population growth rate of this dioecious species may be limited by mate encounter rate, such that below some critical density a colonizing population will fail to establish. We conducted a multi-lake experiment in which H. shoshone was stocked at densities that bracketed our hypothesized critical density of 0.5-5 copoepods/m3. Successful recovery by the copepod was observed only in the lake with the highest initial density (3 copepods/m3). Copepods stocked into small cages at 3000 copepods/m3 survived and reproduced at rates comparable to natural populations, confirming that the lakes were suitable habitat for this species. In support of mate limitation as the mechanism underlying recovery failure, we found a significant positive relationship between mating success and density across experimental and natural H. shoshone populations. Furthermore, a mesocosm experiment provided evidence of increased per capita population growth rate with increasing population density in another diaptomid species, Skistodiaptomus pallidus. Together, these lines of evidence support the importance of the Allee effect to population recovery of H. shoshone in the Sierra Nevada, and to diaptomid copepods in general.     

Type III functional response in Daphnia

The functional response of Daphnia, a common pelagic herbivore in lakes, was assessed with a combination of secondary and meta-analyses of published data and new data from an experiment conducted using very low food levels. Secondary analyses of literature data (28 studies, n = 239-393) revealed a significant positive influence of food concentration on Daphnia clearance rate at low food levels, i.e., evidence of an overall Type III functional response. This result was not an artifact of including data from Daphnia that were exhausted from prolonged food deprivation (more than three hours at very low food). Meta-analysis of Daphnia clearance rate vs. food concentration across a range of low food concentrations (eight studies) showed a significantly positive slope across studies, which also supports the presence of a Type III response. Congruent with these analyses of published data, the feeding experiment showed clear evidence of a Type III functional response for D. pulicaria feeding on Ankistrodesmus falcatus. Food levels at which Daphnia clearance rate declined with decreasing food were near the minimum resource requirement for Daphnia population maintenance at steady state (R*). We suggest that Type III responses are more common than previously believed, perhaps because of the relative paucity of observations at low food levels, and that reduced prey mortality at low phytoplankton densities could be a stabilizing mechanism for Daphnia-phytoplankton systems under resource scarcity.     

Insights into the Porretta Terme (northern Apennines,Italy) hydrothermal system revealed by geochemical data on presently discharging thermal waters and paleofluids

Environmental Geochemistry and Health - This study focuses on the geochemical features of the presently discharging thermal and cold springs and on paleofluids from the upstream portion of the Reno...     

The penetration of formulated guthion® spray through selected fabrics

Abstract

A technique for comparing pesticide penetration through fabric was devised. It involved passing fabric swatches through a controlled spray system and measuring the pesticide residue transferring on and through the tested fabric. Six variations in fabric were selected for testing: 100% cotton woven chambray,

Scotch‐guard^® treated chambray, Tyvek^® , Crowntex^® , and two variations of Gore Tex^®. Guthion^® (azinphos‐methyl) was chosen as the insecticide for controlled use in this experiment because of its widespread use and relatively high toxicity.

Gas Chromatographie analysis of the amount of Guthion^® transferred through the outer fabric was made by the use of analysis of variance (ANOVA) and Duncan's multiple range test. The ANOVA for experiment replication showed no significant difference among the replications of each fabric. The treatment ANOVA was highly significant at the 0.01 level.

Duncan's multiple range test further analyzed the differences in the treatment, and three groups were found to be significantly different from each other. The two types of Gore Tex^®, Tyvek^® and Crowntex^® comprised the group permitting the least penetration. Scotch‐guard^® treated chambray followed, and untreated chambray allowed the greatest penetration.     

Preparation of agricultural residue anion exchangers and its nitrate maximum adsorption capacity

Anion exchangers were prepared from different agricultural residues (AR) after reaction with epichlorohydrin and dimethylamine in the presence of pyridine and N,N-dimethylformamide (EDM method). Agricultural residues anion exchangers (AR-AE) produced by the EDM method were inexpensive and showed almost the same NO₃⁻ removal capacities as Amberlite IRA-900. AR-AE produced from AR with higher hemicelluloses, lignin, ash and extractive contents resulted in the lower yields. Sugarcane bagasse with the highest -cellulose contents of 51.2% had the highest yield (225%) and lowest preparation cost. The highest maximum adsorption capacity (Q_max) for nitrate was obtained from rice hull (1.21 mmol g⁻¹) and pine bark natural exchangers (1.06 mmol g⁻¹). No correlation was found between Q_max and -cellulose content in the original AR. AR-AE produced from different AR demonstrated comparable Q_max due to the removal of non-active compounds such as extractives, lignin and hemicelluloses from AR during the preparation process. Similar preparation from pure cellulose and pure alkaline lignin demonstrated that the EDM method could not produce anion exchangers from pure lignin due to its solubilization after the reaction with epichlorohydrin.     

Metal Levels in Tissues of Florida Gar (Lepisosteus Platyrhincus) from Lake Okeechobee

There is considerable concern about the effects of contaminants on organisms at higher trophic levels, as well as interest in developing bioindicators of ecological health. In this article we examine the levels of arsenic, cadmium, chromium, lead, manganese, mercury, and selenium in the gonads, liver and muscle of Florida gar (Lepisosteus platyrhincus) from Lake Okeechobee in south-central Florida. Gar are top-level predators in freshwater ecosystems. We expected that there would be differences in metal levels as a function of tissue, and predicted differences as a function of sex, size, and location around the lake. There were significant differences among tissues for all metals, but there were few differences as a function of size and gender, which may relate to the generally low levels of metals. Mercury levels were significantly higher in gar collected from the north, and arsenic levels were significantly higher in the gar collected from the south. All metal levels in the muscle of gar collected from Lake Okeechobee were similar to, or lower than those generally reported from other areas of the United States. Thus, although the levels of mercury from the Everglades to the south of Lake Okeechobee are sufficiently high to result in human fish consumption advisories, there are none for Lake Okeechobee. The mercury levels in fish muscle from Lake Okeechobee are lower than from many waters in the U.S. and do not pose a problem for humans. However, liver levels average over the 0.5 microg g(-1) level considered safe for human consumption, and might pose a problem for non-human consumers that eat the fish whole.     

100 years of high GEM concentration in the Central Italian Herbarium and Tropical Herbarium Studies Centre (Florence, Italy)

Up to 1980s, the most used preservative for herbaria specimens was HgCl₂, sublimating at ambient air conditions; ionic Hg then reduces to Hg⁰ (gaseous elemental mercury, GEM) and diffuses throughout poor ventilated environments. High GEM levels may indeed persist for decades, representing a health hazard. In this study, we present new GEM data from the Central Italian Herbarium and Tropical Herbarium Studies Centre of the University of Florence (Italy). These herbaria host one of the largest collection of plants in the world. Here, HgCl₂ was documented as plant preservative up to the 1920s. GEM surveys were conducted in July 2013 and July and December 2017, to account for temporal and seasonal variations.Herbaria show GEM concentrations well above those of external locations, with peak levels within specimen storage cabinets, exceeding 50,000?ng/m³. GEM concentrations up to ~ 7800?ng/m³ were observed where the most ancient collections are stored and no ventilation systems were active. On the contrary, lower GEM concentrations were observed at the first floor. Here, lower and more homogeneously distributed GEM concentrations were measured in 2017 than in 2013 since the air-conditioning system was updated in early 2017.GEM concentrations were similar to other herbaria worldwide and lower than Italian permissible exposure limit of 20,000?ng/m³ (8-hr working day). Our results indicate that after a century from the latest HgCl₂ treatment GEM concentrations are still high, i.e., the treatment itself is almost irreversible. Air conditioning and renewing is probably the less expensive and more effective method for GEM lowering.