A DFT study on the carbamates formation through the absorption of CO2 by AMP

DFT calculations in gas and aqueous solution phases have been performed to study the mechanism of carbamate formation by the absorption of CO₂ in 2-amino-2-methyl-1-propanol (AMP). The results reveal the importance of considering the effect of water as solvent for the reaction to proceed. Furthermore water molecules play an important role as a basic reactant leading to stable intermediates formation. These results point at a single-step, third order reaction as the most probable mechanism for the formation of carbamate by the absorption process.     

Can pine needles indicate trends in the air pollution levels at remote sites?

Data from ten years of integrated monitoring were used here to evaluate whether pine needles are a feasible tool for an assessment of long-term trends of the atmospheric contamination. Pine needles collected once a year were compared to high volume air samples collected for 24 h, every 7 days, and passive air samples integrated over 28-day periods. Results showed the same concentration patterns of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) captured in needles and high volume samples. Passive air samplers were less efficient in sampling the particle-bound compounds. Theoretical air volume equivalent to each needle sample (V_EQ) was calculated as a ratio of the needle concentration over the mean air concentration. Results indicated different equivalent volumes for PAHs and organochlorines, possibly due to the faster degradation rates of PAHs in needles. The most important finding is that in the long term a needle monitoring gives very similar information on temporal trends of the atmospheric pollution as does a high volume air monitoring.     

Occurrence and behaviour of selected hydrophobic alkylphenolic compounds in the Danube River

Six hydrophobic alkylphenolic compounds were investigated for the first time simultaneously in four different matrices in the Danube River. Maximum sediment concentrations were 2.83, 2.10, 0.28, and 0.035 mg kg⁻¹ for nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and octylphenol. Maximum levels in suspended particulate matter (SPM) were 0.18, 0.12, 0.10, and 0.003 mg kg⁻¹. No correlation between concentrations in SPM and sediments was found. Octylphenol monoethoxylate and octylphenol diethoxylate were recorded only in sediment at one location. In mussels and water only nonylphenol and octylphenol were found. Nonylphenol concentrations in mussels (up to 0.34 mg kg⁻¹) correlate with concentrations found in SPM and indicate a slight bioaccumulation. Concentrations in water were close to the limit of quantification. We assume in situ formation of nonylphenol monoethoxylate and nonylphenol in sediments at some locations. In some cases nonylphenol in sediments exceeded the provisional EU environmental quality standards.     

Microbial transformation of synthetic estrogen 17α-ethinylestradiol

Natural estrogens such as estrone, 17β-estradiol, estriol, and the particularly recalcitrant synthetic estrogen 17α-ethinylestradiol used as oral contraceptive, accumulate in the environment and may give rise to health problems. The processes participating in their removal from soil, wastewater, water-sediments, groundwater-aquifer material, and wastewater or sewage treatment plant effluents may involve the action of bacterial and microbial consortia, and in some cases fungi and algae. This review discusses the different efficiencies of bacterial degradation of 17α-ethinylestradiol under aerobic and anaerobic conditions, the role of sulfate-, nitrate-, and iron-reducing conditions in anaerobic degradation, and the role of sorption. The participation of autotrophic ammonia oxidizing bacteria and heterotrophic bacteria in cometabolic degradation of estrogens, the estrogen-degrading action of ligninolytic fungi and their extracellular enzymes (lignin peroxidase, manganese-dependent peroxidase, versatile peroxidase, laccase), and of algae are discussed in detail.     

Conservation Applications of Astronaut Photographs of Earth: Tidal-Flat Loss ( Japan), Elephant Effects on Vegetation (Botswana), and Seagrass and Mangrove Monitoring (Australia)

Abstract: National Aeronautics and Space Administration ( NASA) photographs taken by astronauts from low Earth orbit can provide information relevant to conservation biology. This data source is now more accessible because of improvements in digitizing technology, Internet file transfer, and availability of image processing software. We present three examples of conservation-related projects that benefited from the use of astronaut photographs. First, NASA scientists requested that astronauts photograph the area of the controversial Isahaya Bay reclamation project in Japan. Japanese researchers used photographs from before and after the reclamation as a tool for communication with the public about the effects of tidal-flat loss. The newly acquired images and the availability of high-resolution digital images from NASA archives provided timely public information on the observed changes. Second, we digitally classified and analyzed a Space Shuttle photograph of Chobe National Park in Botswana to identify the locations of woodlands affected by elephants. Field validation later confirmed that areas identified on the image showed evidence of elephant damage. Third, we used a summary map from intensive field surveys of seagrasses in Shoalwater Bay, Australia, as reference data for a supervised classification of a digitized photograph taken from orbit. The classification distinguished seagrasses, sediments, and mangroves with accuracy approximating that in studies using other satellite remote-sensing data. Astronaut photographs are in the public domain, and the database of nearly 400,000 photographs from the late 1960s to the present is available at a single searchable location on the Internet (  http://eol.jsc.nasa.gov/sseop ). These photographs can be used by conservation biologists as a source of general information about the landscape and for quantitative mapping.     

Characteristics of dioxin emissions at startup and shutdown of MSW incinerators

Dioxin concentrations from municipal waste incinerators in Japan and elsewhere often show low concentrations that comply with legal limits (in this paper, the term "dioxin" designates WHO-TEQ: PCDD/Fs+dioxin-like PCB). However, such data is usually generated under normal steady state operational conditions, and there has been little investigation of releases occurring during startup and shutdown. It is important, therefore, to ascertain quantitatively emissions in an unsteady state (startup and shutdown) in order to correctly evaluate the relationship between emissions from a facility and the surrounding environment. The present study aimed to examine dioxin emissions of a continuously operated incinerator at startup and shutdown, and estimating the time period of greatest emission, and the processes causing dioxin generation. The startup process was divided into five stages and the shutdown into two; at each stage, dioxins in the flue gas were measured at the boiler outlet and the stack. From the concentration of dioxins and the flue gas volume at each stage, the amount of dioxins at startup and shutdown were calculated, and these were compared with that under steady state conditions. Dioxin concentration at the stack under steady state conditions was a very low level, while those at startup and shutdown were higher. In the case where dioxin concentration under a steady state is a low level like in this study, it is indicated that the total annual dioxin emission from a facility could be attributed to the startup periods.     

Enhancement of biodegradation of oil adsorbed on fine soils in a bioslurry reactor

Techniques for enhancing the biodegradation of oil-contaminated fine soils in a slurry-phase bioreactor were investigated. Using a model system consisting of kaolin particles containing adsorbed n-dodecane as a diesel fuel surrogate, we investigated how increasing the temperature and adding a surfactant and various hydrophobic support media affected the biodegradation rate of n-dodecane. Increasing the temperature from 25 to 35 degrees C decreased the time required for complete degradation of n-dodecane by 30%, from 110h to 80h. Addition of the surfactant polyethylene glycol p-1,1,3,3-tetramethylbutylphenyl ether decreased the degradation time to less than 48h at 35 degrees C, although a high concentration of the surfactant (3000mgl(-1)) was required. We suspect that the surfactant increased the degradation rate by solubilizing the n-dodecane into the solution phase in which the microorganisms were suspended. We tested five types of organic polymers as support media for the microorganisms and found that the biodegradation time could be reduced by approximately 50% with a support medium made from polyurethane; in the presence of this medium, only 36h was required for complete decomposition at 35 degrees C. The reduction in the degradation time was probably due to transfer of the n-dodecane from the soil to the support medium, which improved contact between the n-dodecane and the microorganisms. The polyurethane support medium bearing the microorganisms was stable and could be reused.     

Distributions,Land-source Input and Atmospheric Fluxes of Methane in Jiaozhou Bay

CH₄ concentrations in both the surface and bottom waters of Jiaozhou Bay were determined during four surveys in 2003, which showed variability with both seasons and tidal cycles. Atmospheric fluxes of CH₄ in Jiaozhou Bay showed obvious seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of CH₄ from Jiaozhou Bay was estimated to be . CH₄ in the water column of Jiaozhou Bay was found to come from several land-sources including riverine water input, sewage water input and groundwater input. The spatial and temporal variation in distributions and atmospheric fluxes of CH₄ in Jiaozhou Bay was influenced mainly by the input of polluted river waters and the sewage effluents along the eastern coast, which highlights the effects of human impacts on CH₄ emission rates.     

Determination of nonylphenol ethoxylates and octylphenol ethoxylates in environmental samples using 13C-labeled surrogate compounds

Alkylphenol polyethoxylates (APEOs) have been widely used as nonionic surfactants in a variety of industrial and commercial products. Typical compounds are nonylphenol polyethoxylates (NPEOs) and octylphenol polyethoxylates (OPEOs), which serve as precursors to nonylphenol (NP) and octylphenol (OP), respectively. NP and 4-t-OP are known to have endocrine disrupting effects on fish (medaka, Oryzias latipes), so it is important to know the concentrations of APEOs in the environment. Because the analytical characteristics of these compounds depend on the length of the ethoxy chain, it is necessary to use appropriate compounds as internal standards or surrogates. We synthesized two 13C-labeled surrogate compounds and used these compounds as internal standards to determine NPEOs and OPEOs by high-performance liquid chromatography (LC)-mass spectrometry. Method detection limits were 0.015 microg/L for NP (2)EO to 0.037 microg/L for NP(12)EO, and 0.011 microg/L for OP(3,6)EO to 0.024 microg/L for OP (4)EO. NPEO concentrations in water from a sewage treatment plant were less than 0.05-0.52 microg/L for final effluent and 1.2-15 microg/L for influent. OPEO concentrations were less than 0.05-0.15 microg/L for the final effluent and less than 0.05-1.1 microg/L for influent.     

Historical eutrophication in a river-estuary complex in mid-coast Maine.

European settlement of New England brought about a novel disturbance regime that impacted rivers and estuaries through overfishing, deforestation, dams, and water pollution. The negative consequences of these activities intensified with industrialization in the 19th and 20th centuries, often resulting in ecosystem degradation. Since environmental legislation was implemented in the 1970s, improvement in water quality has been tangible and widespread; however, ecological recovery can require substantial amounts of time and may never be complete. To document the natural baseline conditions and investigate the recovery of a severely degraded river-estuary complex in mid-coast Maine, we examined diatoms, pollen, total organic carbon, total nitrogen, stable isotopes, total phosphorus, biogenic silica, and trace metals in intertidal sediments and established a chronology with 14C, 210Pb, and indicator pollen horizons. Both climate variability and human effects were evident in the sedimentary record of Merrymeeting Bay, the freshwater tidal portion of the Kennebec estuary. Natural climate variability was apparent in an episode of high sedimentation and altered diatom abundance during the 12th and 13th centuries and in changing pollen abundances between the 16th and 19th centuries, indicative of regional cooling. During the 18th century, colonial land clearance began an era of high sedimentation and eutrophication that strongly intensified with industrialization during the late 19th and 20th centuries. Improvements in water quality over the past 30 years in response to environmental regulation had little effect on ecosystem recovery as represented by the sedimentary record. Diatom composition and productivity and high fluxes of organic C, total P, and biogenic Si in recent sediments indicate that rates of nutrient loading remain high. These environmental proxies imply that aquatic productivity in Merrymeeting Bay was originally nutrient limited and water clarity high, relative to today. Further recovery may require more stringent regulation of nutrient inputs from industrial and municipal point sources. This historical study can contribute to public debate about the environmental management of this unusual river-estuary complex by describing its long-term natural baseline, thereby illustrating the upper limit of its potential for recovery.