Chemical characterization of fine aerosols in respect to water-soluble ions at the eastern Middle Adriatic coast

Fine particulate matter (PM2.5) concentrations at the Middle Adriatic coastal site of Croatia were affected by different air-mass inflows and/or local sources and meteorological conditions, and peaked in summer. More polluted continental air-mass inflows mostly affected the area in the winter period, while southern marine pathways had higher impact in spring and summer. Chemical characterization of the water-soluble inorganic and organic ionic constituents is discussed with respect to seasonal trends, possible sources, and air-mass inputs. The largest contributors to the PM2.5 mass were sea salts modified by the presence of secondary sulfate-rich aerosols indicated also by principal component analysis. SO42− was the prevailing anion, while the anthropogenic SO42− (anth-nssSO42−) dominantly constituted the major non-sea-salt SO42− (nssSO42−) fraction. Being influenced by the marine origin, its biogenic fraction (bio-nssSO42−) increased particularly in the spring. During the investigated period, aerosols were generally acidic. High Cl− deficit was observed at Middle Adriatic location for which the acid displacement is primarily responsible. With nssSO42− being dominant in Cl− depletion, sulfur-containing species from anthropogenic pollution emissions may have profound impact on atmospheric composition through altering chlorine chemistry in this region. However, when accounting for the neutralization of H2SO4 by NH3, the potential of HNO3 and organic acids to considerably influence Cl− depletion is shown to increase. Intensive open-fire events substantially increased the PM2.5 concentrations and changed the water-soluble ion composition and aerosol acidity in summer of 2015. To our knowledge, this work presents the first time-resolved data evaluating the seasonal composition of water-soluble ions and their possible sources in PM2.5 at the Middle Adriatic area. This study contributes towards a better understanding of atmospheric composition in the coastal Adriatic area and serves as a basis for the comparison with future studies related to the air quality at the coastal Adriatic and/or Mediterranean regions.     

Landscape consequences of aggregation rules for functional equivalence in compensatory mitigation programs

Mitigation and offset programs designed to compensate for ecosystem function losses due to development must balance losses from affected ecosystems with gains in restored ecosystems. Aggregation rules applied to ecosystem functions to assess site equivalence are based on implicit assumptions about the substitutability of functions among sites and can profoundly influence the distribution of restored ecosystem functions on the landscape. We investigated the consequences of rules applied to the aggregation of ecosystem functions for wetland offsets in the Beaverhill watershed in Alberta, Canada. We considered the fate of 3 ecosystem functions: hydrology, water purification, and biodiversity. We set up an affect‐and‐offset algorithm to simulate the effect of aggregation rules on ecosystem function for wetland offsets. Cobenefits and trade‐offs among functions and the constraints posed by the quantity and quality of restorable sites resulted in a redistribution of functions between affected and offset wetlands. Hydrology and water purification functions were positively correlated with one another and negatively correlated with biodiversity function. Weighted‐average rules did not replace functions in proportion to their weights. Rules prioritizing biodiversity function led to more monofunctional wetlands and landscapes. The minimum rule, for which the wetland score was equal to the worst performing function, promoted multifunctional wetlands and landscapes. The maximum rule, for which the wetland score was equal to the best performing function, promoted monofunctional wetlands and multifunctional landscapes. Because of implicit trade‐offs among ecosystem functions, no‐net‐loss objectives for multiple functions should be constructed within a landscape context. Based on our results, we suggest criteria for the design of aggregation rules for no net loss of ecosystem functions within a landscape context include the concepts of substitutability, cobenefits and trade‐offs, landscape constraints, heterogeneity, and the precautionary principle.     

Alginate beads containing water treatment residuals for arsenic removal from water—formation and adsorption studies

Water treatment residuals (WTRs) produced in large quantities during deironing and demanganization of infiltration water, due to high content of iron and manganese oxides, exhibit excellent sorptive properties toward arsenate and arsenite. Nonetheless, since they consist of microparticles, their practical use as an adsorbent is limited by difficulties with separation from treated solutions. The aim of this study was entrapment of chemically pretreated WTR into calcium alginate polymer and examination of sorptive properties of the obtained composite sorbent toward As(III) and As(V). Different products were formed varying in WTR content as well as in density of alginate matrix. In order to determine the key parameters of the adsorption process, both equilibrium and kinetic studies were conducted. The best properties were exhibited by a sorbent containing 5 % residuals, formed in alginate solution with a concentration of 1 %. In slightly acidic conditions (pH 4.5), its maximum sorption capacity was 3.4 and 2.9 mg g^?1 for As(III) and As(V), respectively. At neutral pH, the adsorption effectiveness decreased to 3.3 mg As g^?1 for arsenites and to 0.7 mg As g^?1 for arsenates. The presence of carboxylic groups in polymer chains impeded in neutral conditions the diffusion of anions into sorbent beads; therefore, the main rate-limiting step of the adsorption, mainly in the case of arsenates, was intraparticle diffusion. The optimal condition for simultaneous removal of arsenates and arsenites from water by means of the obtained composite sorbent is slightly acidic pH, ensuring similar adsorption effectiveness for both arsenic species.     

Oxygen demand for the stabilization of the organic fraction of municipal solid waste in passively aerated bioreactors

Conventional aerobic waste treatment technologies require the use of aeration devices that actively transport air through the stabilized waste mass, which greatly increases operating costs. In addition, improperly operated active aeration systems, may have the adverse effect of cooling the stabilized biomass. Because active aeration can be a limiting factor for the stabilization process, passive aeration can be equally effective and less expensive. Unfortunately, there are few reports documenting the use of passive aeration systems in municipal waste stabilization. There have been doubts raised as to whether a passive aeration system provides enough oxygen to the organic matter mineralization processes. In this paper, the effectiveness of aeration during aerobic stabilization of four different organic fractions of municipal waste in a reactor with an integrated passive ventilation system and leachate recirculation was analyzed. For the study, four fractions separated by a rotary screen were chosen. Despite the high temperatures in the reactor, the air flow rate was below 0.016 m³/h. Using Darcy’s equation, theoretical values of the air flow rate were estimated, depending on the intensity of microbial metabolism and the amount of oxygen required for the oxidation of organic compounds. Calculations showed that the volume of supplied air exceeded the microorganisms demand for oxidation and endogenous activity by 1.7–2.88-fold.     

Proposal for selective differentiating of nerve agent G and V type with utilisation of modified Ellman’s method

We studied issues of organophosphorus agents’ analysis. Immobilised enzyme–inhibitors complexes (e.g. acetylcholinesterase-organophosphate nerve agent) were studied with modified Ellman’s biochemical method utilised for assessment of acetylcholinesterase activity. Biochemical reactions are widespread and they are the most frequent used analytical methods for determination of nerve agents. This modified method is based on the nucleophilic reactions of mono- and bispyridinium aldoximes of a type 2-PAM, MMB-4 and HI-6, their homologues and isomers with enzyme–inhibitor complexes. The procedure for a gradual analysis of G and V type, Sarin, Cyclohexylsarin, Soman, Tabun, agent VX and R-33 was proposed in terms of studied nucleophilic substitution reactions quantification results. This method enables selective determination of these chemical warfare agents. A gradual analysis was evaluated by statistic method of probabilistic calculus. This type of analysis can be used for assessment of acetylcholinesterase inhibitors in very low concentrations close to hygienic limits.     

Micronucleus frequency in sheep lymphocytes after in vitro exposure to fungicide tolylfluanid

The fungicide tolylfluanid (N - dichlorofluoromethylthio-N′, N - dimethyl - N - p - tolylsulfamide), was investigated by cytokinesis-block micronucleus assay. Tolylfluanid at the lowest concentration (1 × 10^{? 6}mol L^{? 1})did not influence significantly the frequency of micronuclei in sheep lymphocyte cultures in comparison with control (32.33 ± 3.51/1000 binucleated cells versus 30.33 ± 2.82/1000 binucleated cells in dimethylsulfoxide (DMSO) control, P = 0.44). Higher tolylfluanid concentrations (1 × 10^{? 4} and, 1 × 10^{? 5} mol L^{? 1}) resulted in a significant dose-dependent increase in the number of micronuclei in comparison with control (74.00 ± 13.00/1000 binucleated cells and 52.67 ± 10.12/1000 binucleated cells versus 30.33 ± 2. 82/1000 binucleated cells in DMSO control, P = 0.005 and 0.02, respectively, ANOVA followed by Tukey test P < 0.05). Many of the treated cells also possessed multiple micronuclei. Tolylfluanid did not affect the nuclear division index at all treatment concentrations. Our in vitro results thus demonstrate that tolylfluanid had a significant genotoxic effect at only the highest concentration tested.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

Climate adaptation of biodiversity conservation in managed forest landscapes

Conservation of biodiversity in managed forest landscapes needs to be complemented with new approaches given the threat from rapid climate change. Most frameworks for adaptation of biodiversity conservation to climate change include two major strategies. The first is the resistance strategy, which focuses on actions to increase the capacity of species and communities to resist change. The second is the transformation strategy and includes actions that ease the transformation of communities to a set of species that are well adapted to the novel environmental conditions. We suggest a number of concrete actions policy makers and managers can take. Under the resistance strategy, five tools are introduced, including: identifying and protecting forest climate refugia with cold-favored species; reducing the effects of drought by protecting the hydrological network; and actively removing competitors when they threaten cold-favored species. Under the transformation strategy, we suggest three tools, including: enhancing conditions for forest species favored by the new climate, but currently disfavored by forest management, by planting them at suitable sites outside their main range; and increasing connectivity across the landscape to enhance the expansion of warm-favored species to sites that have become suitable. Finally, we suggest applying a landscape perspective and simultaneously managing for both retreating and expanding species. The two different strategies (resistance and transformation) should be seen as complementary ways to maintain a rich biodiversity in future forest ecosystems.     

Ameliorative effects of deferiprone and tetraethylammonium salt of salinomycinic acid on lead-induced toxicity in mouse testes

Environmental Science and Pollution Research - In this study, we compare the effects of deferiprone (Def) and tetraethylammonium salt of salinomycinic acid (Sal) on lead (Pb)-induced toxicity in...