Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.     

Effects of initial saturation on properties modification and displacement of tetrachloroethene with aqueous isobutanol

Packed column experiments were conducted to study effects of initial saturation of tetrachloroethene (PCE) in the range of 1.0-14% pore volume (PV) on mobilization and downward migration of the non-aqueous phase liquid (NAPL) product upon contact with aqueous isobutanol ( approximately 10 vol.%). This study focused on the consequences of swelling beyond residual saturation. Columns were packed with mixtures of neat PCE, water and glass beads and waterflooded to establish a desired homogeneous residual saturation, and then flooded with aqueous isobutanol under controlled hydraulic conditions. Results showed a critical saturation of approximately 8% PV for these packed column experimental conditions. At low initial PCE saturations (<8% PV), experimental results showed reduced risk of NAPL-product migration upon contact with aqueous isobutanol. At higher initial PCE saturations (>8% PV), results showed NAPL-product mobilization and downward migration which was attributed to interfacial tension (IFT) reduction, swelling of the NAPL-product, and reduced density modification. Packed column results were compared with good agreement to theoretical predictions of NAPL-product mobilization using the total trapping number, N(T). In addition to the packed column study, preliminary batch experiments were conducted to study the effects of PCE volumetric fraction in the range of 0.5-20% on density, viscosity, and IFT modification as a function of time following contact with aqueous isobutanol ( approximately 10 vol.%). Modified NAPL-product fluid properties approached equilibrium within approximately 2 h of contact for density and viscosity. IFT reduction occurred immediately as expected. Measured fluid properties were compared with good agreement to theoretical equilibrium predictions based on UNIQUAC. Overall, this study demonstrates the importance of initial DNAPL saturation, and the associated risk of downward NAPL-product migration, in applying alcohol flooding for remediation of DNAPL contaminated ground water sites.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.     

Evaluation of heavy metal acute toxicity and bioaccumulation in soil ciliated protozoa

Laboratory toxicity tests, using ciliated protozoa, are scarce and they have been carried out usually with freshwater species. In this study, we have analysed the acute cytotoxicity of Cd, Zn and Cu in five different strains of very common soil ciliate species (Colpoda steinii, Colpoda inflata and Cyrtolophosis elongata), which were isolated from very different soil samples (polluted or not with heavy metals). Soil ciliates are quite resistant to heavy metals pollution with regard to ciliates from other habitats. The toxicity sequence was Cd>Cu>Zn. Results from Cd+Zn mixtures indicated that Cd cytotoxicity decreases in the presence of low or moderate Zn concentrations. A broad heavy metal resistance level diversity exists among isolates of colpodid ciliates and it is seen to be a genetic feature rather than a habitat dependence. Bioaccumulation is seen to be the main mechanism involved in the metal resistance, except for Cu. For the first time in ciliates, a fluorescent method has been applied to detect Zn intracellular deposits. This methodology might be an useful tool for monitoring heavy metal pollution in soils.     

Adjusting the effect of seasonal variability in the bioassessment of streams

Bioassessment tools should distinguish between the effects of anthropogenic degradation in communities and natural temporal changes. The present study tests the influence of natural seasonal variability on macroinvertebrate stream communities assessed by a predictive model (PORTRIV) and a multimetric index (IPtI) calibrated for spring. The scores of PORTRIV decreased significantly between spring and autumn, and between spring and winter (ca. 37 to 53 %, respectively), while those of IPtI did not change significantly between seasons. For non-reference samples, the results of the predictive model also indicate no significant differences. A correction factor (CF) was calculated to adjust the existing differences in the model assessments between seasons, based on the percentage of variation of reference site scores from spring to autumn and winter. After the application of the CF to the OE50 scores of spring reference samples, the differences were no longer significant. Independent reference validation sites confirmed this tendency. This method has the advantage of avoiding large efforts required for the construction of databases from other seasons and the development of new models to allow the assessment of streams in seasons other than spring. Further tests with models developed in regions with more marked seasonal changes should be done to confirm its wider applicability.     

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

Baked Foams Based on Cassava Starch Coated with Polyvinyl Alcohol with a Higher Degree of Hydrolysis

The aims of this work were to produce trays based on cassava starch, coated with polyvinyl alcohol (PVA) with a higher degree of hydrolysis (98%), and to study the effects of the coating on the mechanical and water sorption properties of the trays. Two types of PVA were tested: SELVOL? 325 (degree of polymerization?=?1000–1500) and SELVOL? 107 (degree of polymerization?=?350–650). A decrease in the water absorption capacity of 50% was observed when the coated samples were compared with the control sample after 30 min of immersion in water. It was observed in both coated samples a reduction of the initial rate of water adsorption sorption and a decrease in hydrophilicity compared with the control sample. Tensile strength and elongation were increased with application of the coatings. The use of the two types of PVA resulted in materials with similar mechanical and water sorption properties.     

Microplastic distribution in surface sediments along the Spanish Mediterranean continental shelf

Environmental Science and Pollution Research - Microplastics (MPs) are widely recognised as a contaminant of emerging concern in the marine environment. This work provides original data of the...     

Assessing ecological function in the context of species recovery

Species interactions matter to conservation. Setting an ambitious recovery target for a species requires considering the size, density, and demographic structure of its populations such that they fulfill the interactions, roles, and functions of the species in the ecosystems in which they are embedded. A recently proposed framework for an International Union for Conservation of Nature Green List of Species formalizes this requirement by defining a fully recovered species in terms of representation, viability, and functionality. Defining and quantifying ecological function from the viewpoint of species recovery is challenging in concept and application, but also an opportunity to insert ecological theory into conservation practice. We propose 2 complementary approaches to assessing a species’ ecological functions: confirmation (listing interactions of the species, identifying ecological processes and other species involved in these interactions, and quantifying the extent to which the species contributes to the identified ecological process) and elimination (inferring functionality by ruling out symptoms of reduced functionality, analogous to the red-list approach that focuses on symptoms of reduced viability). Despite the challenges, incorporation of functionality into species recovery planning is possible in most cases and it is essential to a conservation vision that goes beyond preventing extinctions and aims to restore a species to levels beyond what is required for its viability. This vision focuses on conservation and recovery at the species level and sees species as embedded in ecosystems, influencing and being influenced by the processes in those ecosystems. Thus, it connects and integrates conservation at the species and ecosystem levels.