Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

Hypoxia in the Baltic Sea: Biogeochemical Cycles, Benthic Fauna, and Management

Hypoxia has occurred intermittently over the Holocene in the Baltic Sea, but the recent expansion from less than 10 000 km² before 1950 to >60 000 km² since 2000 is mainly caused by enhanced nutrient inputs from land and atmosphere. With worsening hypoxia, the role of sediments changes from nitrogen removal to nitrogen release as ammonium. At present, denitrification in the water column and sediments is equally important. Phosphorus is currently buried in sediments mainly in organic form, with an additional contribution of reduced Fe-phosphate minerals in the deep anoxic basins. Upon the transition to oxic conditions, a significant proportion of the organic phosphorus will be remineralized, with the phosphorus then being bound to iron oxides. This iron-oxide bound phosphorus is readily released to the water column upon the onset of hypoxia again. Important ecosystems services carried out by the benthic fauna, including biogeochemical feedback-loops and biomass production, are also lost with hypoxia. The results provide quantitative knowledge of nutrient release and recycling processes under various environmental conditions in support of decision support tools underlying the Baltic Sea Action Plan.     

Reduction of Baltic Sea Nutrient Inputs and Allocation of Abatement Costs Within the Baltic Sea Catchment

The Baltic Sea Action Plan (BSAP) requires tools to simulate effects and costs of various nutrient abatement strategies. Hierarchically connected databases and models of the entire catchment have been created to allow decision makers to view scenarios via the decision support system NEST. Increased intensity in agriculture in transient countries would result in increased nutrient loads to the Baltic Sea, particularly from Poland, the Baltic States, and Russia. Nutrient retentions are high, which means that the nutrient reduction goals of 135 000 tons N and 15 000 tons P, as formulated in the BSAP from 2007, correspond to a reduction in nutrient loadings to watersheds by 675 000 tons N and 158 000 tons P. A cost-minimization model was used to allocate nutrient reductions to measures and countries where the costs for reducing loads are low. The minimum annual cost to meet BSAP basin targets is estimated to 4.7 billion €.     

Forest Die-Back Modified Plankton Recovery from Acidic Stress

We examined long-term data on water chemistry of Lake Rachelsee (Germany) following the changes in acidic depositions in central Europe since 1980s. Despite gradual chemical recovery of Rachelsee, its biological recovery was delayed. In 1999, lake recovery was abruptly reversed by a coincident forest die-back, which resulted in elevated terrestrial export of nitrate and ionic aluminum lasting ~5 years. This re-acidification episode provided unique opportunity to study plankton recovery in the rapidly recovering lake water after the abrupt decline in nitrate leaching from the catchment. There were sudden changes both in lake water chemistry and in plankton biomass structure, such as decreased bacterial filaments, increased phytoplankton biomass, and rotifer abundance. The shift from dominance of heterotrophic to autotrophic organisms suggested their substantial release from severe phosphorus stress. Such a rapid change in plankton structure in a lake recovering from acidity has, to the best of our knowledge, not been previously documented.     

Dioxin-like activity in sediments from Tai Lake, China determined by use of the H4IIE-luc bioassay and quantification of individual AhR agonists

Deterioration of the general ecosystem and specifically quality of the water in Tai Lake (Ch: Taihu), the third largest freshwater in China, is of great concern. However, knowledge on status and trends of dioxin-like compounds in Tai Lake was limited. This study investigated AhR-mediated potency and quantified potential aryl hydrocarbon receptor (AhR) agonists in sediments from four regions (Meiliang Bay, Zhushan Lake, Lake Center, Corner of Zhushan Lake, and Meiliang Bay) of Tai Lake by use of the in vitro H4IIE-luc, cell-based, transactivation, reporter gene assay, and instrumental analysis. Concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (Bio-TEQs) in sediments ranged from less than the limit of detection to 114.5 pg/g, dry weight, which indicated that organic extracts of sediments exhibited significant AhR-mediated potencies. Results of the potency balance analysis demonstrated that acid-labile, dioxin-like compounds represented a greater proportion of concentrations of Bio-TEQs in sediments from Tai Lake. Concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents calculated as the sum of the product of concentrations of individual congeners and their respective relative potencies (Chem-TEQs) based on polycyclic aromatic hydrocarbons and/or polychlorinated biphenyls represented no more than 10 % of the total concentrations of Bio-TEQs.     

A comparison of statistical methods for deriving freshwater quality criteria for the protection of aquatic organisms

Species sensitivity distributions (SSDs) are increasingly used in both ecological risk assessment and derivation of water quality criteria. However, there has been debate about the choice of an appropriate approach for derivation of water quality criteria based on SSDs because the various methods can generate different values. The objective of this study was to compare the differences among various methods. Data sets of acute toxicities of 12 substances to aquatic organisms, representing a range of classes with different modes of action, were studied. Nine typical statistical approaches, including parametric and nonparametric methods, were used to construct SSDs for 12 chemicals. Water quality criteria, expressed as hazardous concentration for 5 % of species (HC₅), were derived by use of several approaches. All approaches produced comparable results, and the data generated by the different approaches were significantly correlated. Variability among estimates of HC₅ of all inclusive species decreased with increasing sample size, and variability was similar among the statistical methods applied. Of the statistical methods selected, the bootstrap method represented the best-fitting model for all chemicals, while log-triangle and Weibull were the best models among the parametric methods evaluated. The bootstrap method was the primary choice to derive water quality criteria when data points are sufficient (more than 20). If the available data are few, all other methods should be constructed, and that which best describes the distribution of the data was selected.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Effect of ibuprofen exposure on blood,gill, liver,and brain on common carp (Cyprinus carpio) using oxidative stress biomarkers

Although trace concentrations of ibuprofen (IBP) have been detected in diverse water bodies, there is currently insufficient information on the potentially deleterious effects of this xenobiotic. The present study aimed to determine whether IBP induces oxidative stress in brain, liver, gill, and blood of the common carp Cyprinus carpio. To this end, the median lethal concentration at 96 h (96-h LC₅₀) was determined and the lowest observed adverse effect level was established. Carp were exposed to the latter concentration (17.6 mg L^?1) for 12, 24, 48, 72, and 96 h, and the following biomarkers were evaluated: lipid peroxidation (LPX) and activity of the antioxidant enzymes superoxide dismutase, catalase, and glutathione peroxidase. Results indicated that LPX and antioxidant enzymes’ activity increased significantly (p?<?0.05) with respect to the control group in liver, gill, and blood, while no significant differences occurred in brain. In conclusion, IBP induced oxidative stress on C. carpio, the liver being the organ most affected by this damage.     

Bioremediation assessment of diesel–biodiesel-contaminated soil using an alternative bioaugmentation strategy

This study investigated the effectiveness of successive bioaugmentation, conventional bioaugmentation, and biostimulation of biodegradation of B10 in soil. In addition, the structure of the soil microbial community was assessed by polymerase chain reaction-denaturing gradient gel electrophoresis. The consortium was inoculated on the initial and the 11th day of incubation for successive bioaugmentation and only on the initial day for bioaugmentation and conventional bioaugmentation. The experiment was conducted for 32 days. The microbial consortium was identified based on sequencing of 16S rRNA gene and consisted as Pseudomonas aeruginosa, Achromobacter xylosoxidans, and Ochrobactrum intermedium. Nutrient introduction (biostimulation) promoted a positive effect on microbial populations. The results indicate that the edaphic community structure and dynamics were different according to the treatments employed. CO₂ evolution demonstrated no significant difference in soil microbial activity between biostimulation and bioaugmentation treatments. The total petroleum hydrocarbon (TPH) analysis indicated a biodegradation level of 35.7 and 32.2 % for the biostimulation and successive bioaugmentation treatments, respectively. Successive bioaugmentation displayed positive effects on biodegradation, with a substantial reduction in TPH levels.     

The amorphous Zn biomineralization at Naracauli stream,Sardinia: electron microscopy and X-ray absorption spectroscopy

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.