Toxicological and chemical assessment of ordinance compounds in marine sediments and porewaters

Toxicological and chemical studies were performed with a silty and a sandy marine sediment spiked with 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrophenylmethylnitramine (tetryl), or 2,4,6-trinitrophenol (picric acid). Whole sediment toxicity was analyzed by the 10-day survival test with the amphipod Ampelisca abdita, and porewater toxicity tests assessed macro-algae (Ulva fasciata) zoospore germination and germling growth, sea urchin (Arbacia punctulata) embryological development, and polychaete (Dinophilus gyrociliatus) survival and reproduction. Whole sediments spiked with 2,6-DNT were not toxic to amphipods. The fine-grained sediment spiked with tetryl was also not acutely toxic. The tetryl and picric acid LC50 values in the sandy sediment were 3.24 and 144 mg/kg dry weight, respectively. The fine-grained sediment spiked with picric acid generated a U-shaped concentration-response curve in the amphipod test, with increased survival both in the lowest and highest concentration. Grain-size distribution and organic carbon content strongly influenced the behavior of ordnance compounds in spiked sediments. Very low concentrations were measured in some of the treatments and irreversible binding and biodegradation are suggested as the processes responsible for the low measurements. Porewater toxicity varied with its sedimentary origin and with ordnance compound. The sea urchin embryological development test tended to be the least sensitive. Tetryl was the most toxic chemical in all porewater tests, and picric acid the least toxic. Samples spiked with 2,6-DNT contained a degradation product identified as 2-methyl-3-nitroaniline (also known as 2-amino-6-nitrotoluene), and unidentified peaks, possibly degradation products, were also seen in some of the picric acid- and tetryl-spiked samples. Degradation products may have played a role in observed toxicity.     

The Role of Naturally Occurring River Biofilms on the Degradation Kinetics of Diazinon

River biofilms are dominant riverine biota with diverse microorganisms. They have been found to contribute greatly to river self‐purification for removal of nutrients and organic matter. This study intended to investigate the ability of naturally occurring river biofilms with changing seasons for the removal of the organophosphorus pesticide diazinon. Natural river biofilms from spring showed higher ability to remove diazinon (99.9% removal) than those from winter (77%) with light exposure. In contrast to control sets without biofilms under irradiation, 27% of diazinon removal in spring and 22% in winter may result from microbial activity within biofilms. Removal of diazinon by river biofilms could be attributed mostly to degradation due to low sorption capacity of biofilms. Spring biofilms had higher dissipation rates (0.265 and 0.486 d^?1 for biofilms with different growth periods) than winter ones (0.099 and 0.119 d^?1) according to first order model. Higher ability of diazinon removal by spring biofilms may be explained by their higher bacterial and algal biomass comparing to winter biofilms. Naturally occurring river biofilms played a significant role in degradation of diazinon, particularly for those grown in spring. Their potential for use in the treatment of diazinon‐contaminated water has been demonstrated.     

Spatio-temporal variation in soil seed banks under contrasting grazing regimes following low and high seasonal rainfall in arid Namibia

In arid rangelands, soil seed bank characteristics vary with rainfall patterns, livestock pressure and habitat heterogeneity. We investigated this issue by assessing spatio-temporal patterns in soil seed bank density and richness in a degraded (heavy grazing) and non-degraded (light grazing) Nama Karoo ecosystem. To account for variation in seed distribution, different microsites were compared, and the effect of diaspore size on the patterning analyzed. Long-term heavy grazing increased seed densities and species richness of the soil seed bank by favoring small-seeded and tiny-seeded annual species. The spatial patterning of the soil seed bank was, however, similar to that found under sustainable grazing. The overall seed distribution was dictated by the small-scale environmental heterogeneity, which interacted with diaspore size. Our results suggest that the degraded environment is still efficient in controlling secondary dispersal and retaining seeds. This is through low stature barriers like surface rocks, which replace the function of grazing-sensitive perennial grasses in trapping and storing small diaspores. Soil seed banks were persistent and accumulated readily-germinable seeds over time. Observed temporal pattern across the study sites indicates that both condition and sequence of preceding rainfall seasons are likely to have a profound effect on soil seed banks of subsequent years.     

Degradation of High Mountain Ecosystems in Northern Europe

Data material of a long-term high mountain ecosystem research project was used to interpret the grazing impact of reindeers. In central Norway investigations were conducted to both, areas where reindeer grazing is excluded, and areas where intensive pasturing is present for a long period of time.The comparative analysis of grazing impact was based on similar environmental conditions. The results were transposed to northern Norway where dramatic overgrazing had been exceeding the carrying capacity. Using landscape ecological mappings, especially of vegetation and soils, the impact of reindeer grazing in different areas became obvious. Non-grazed lichen-dominated ecosystems of the snow-free locations functioned sensitively near the limit of organism survival. These localities were most influenced by grazing as they offer the winter forage to the reindeers. So, intensive grazing in central Norway led to landscape degradation by destruction of the vegetation and superinduced by soil erosion. Those features were comparable to the situation in northern Norway, where a broad-scale destruction of the environment combined with a depression of the altitudinal belts had occurred due to overgrazing. Functioning principles of intact high mountain systems were explained and used to interpret the environmental background for the understanding of degradation phenomena. Finally, the use of a new model calculating the carrying capacity of high mountain landscape was discussed.     

Biodegradation of CO2, CH4 and volatile organic compounds (VOCs) in soil gas from the Vicano–Cimino hydrothermal system (central Italy)

We investigated the effect of microbial activity on the chemistry of hydrothermal fluids related to the Vicano–Cimino system, central Italy. The database included the composition and δ¹³C CO₂ and δ¹³C CH₄ values for soil gas from an area characterized by intense degassing of fluids having a deep origin. The δ¹³C CH₄ values along vertical profiles in the soil indicated that CH₄ was controlled by microbial oxidation occurring at shallow (< 50 cm) depth, where free O₂ was available. This was consistent with the vertical gradients of CH₄, H₂S and O₂ concentrations. The δ¹³C CO₂ values in soil gas, characterized by a composition similar to that of the hydrothermal fluids, were not significantly influenced by biodegradation. On the contrary, gas strongly affected by air contamination showed a significant δ¹³C CO₂ fractionation. Microbial activity caused strong consumption of hydrothermal alkanes, alkenes, cyclics and hydrogenated halocarbons, whereas benzene was recalcitrant. Oxygenated compounds from hydrocarbon degradation consisted of alcohols, with minor aldehydes, ketones and carboxylic acids. A predominance of alcohols at a high rate of degassing flux, corresponding to a short residence time of hydrothermal gas within the soil, indicated incomplete oxidation. N-bearing compounds were likely produced by humic substances in the soil and/or related to contamination by pesticides, whereas α-pinene traced air entering the soil. The study demonstrates that microbial communities in the soil play an important role for mitigating the release to the atmosphere of C-bearing gases, especially CH₄, through diffuse soil degassing, a mechanism that in central Italy significantly contributes to the discharge of CO₂-rich gas from deep sources.     

An evaluation on the degradation evolutions in three constitutive models for bonded geomaterials by DEM analyses

This paper presents a numerical evaluation on the degradation evolutions in three well-known constitutive models for bonded geomaterials using the Distinct Element Method (DEM). A series of isotropic, constant stress ratio and biaxial compression tests on the bonded geomaterials were carried out by a two-dimensional (2D) DEM code, NS2D, for this purpose. The constitutive models examined are the disturbed state constitutive model (DSC model), the superloading yield surface model and Nova’s model. First, a microscopic interpretation of the degradation variable, which is used to describe the degradation evolution in the models, was presented based on the micromechanics theory to compare the degradation evolutions used by the models with the DEM results. Then, the macromechanical responses of the numerical specimens in the DEM tests were examined in comparison with the experimental data on the artificially bonded sands. Finally, the degradation evolutions observed in the DEM tests were compared with the results predicted by the constitutive models. The study shows that the DEM results are able to capture the main features of the artificially bonded sands. The degradation evolutions used in the three constitutive models are all overally in agreement with the DEM results. In addition, two simple evolution equations for the degradation variable, which can well describe the degradation evolution observed in the DEM tests, were presented and discussed.     

Degradation of Bezafibrate with UV/H2O2 in Surface Water and Wastewater Treatment Plant Effluent

Bezafibrate (BZF), a widely used lipid regulator, is a potential threat to ecosystems and human health in water, and the recent research showed that advanced oxidation processes (AOPs) are much more effective for BZF degradation. In this study, we investigated the photochemical decomposition of BZF in surface water and effluent from waste water treatment plants (WWTP) by UV/H₂O₂ process. The results showed that the UV/H₂O₂ process was a promising method to remove BZF at low concentration, generally at µg L^?1 level. When initial concentrations reach 100 µg L^?1 in the deionized water, >99.8% of BZF could be removed in 16 min under UV intensity of 61.4 µm cm^?2, at the H₂O₂ concentration of 0.1 mg L^?1, and neutral pH condition. Moreover, BZF degradation was inhibited in this process when humic acid (HA) and inorganic solution anions were added to the deionized water solutions, including chloride, nitrate, bicarbonate, and sulfate, significantly. In the surface water and effluent of WWTP, however, the removal efficiency of BZF was lower than that in the deionized water because of the interference of complex constituents in the surface water and effluent. Some main intermediates at the m/z range of 100–400 were observed by high performance LC‐MS (HPLC/MS) and a simple pathway of BZF degradation by UV/H₂O₂ was proposed.     

Quantification of Diclofenac in Hospital Effluent and Identification of Metabolites and Degradation Products

In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10^?3 mol L^?1, and phase B was methanol (5 × 10^?3 mol L^?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L^?1, the LQs, 8.3 and 0.05 µg L^?1, and the linear range from 10 up to 2000 µg L^?1 and 0.05 up to 10 µg L^?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.