HE PHASE TRANSFER OF CO(II) CATALYZED BY 2,2 '-BIPYRIDINE AT THE WATER/NITROBENZENE INTERFACE

The chemical reactions coupled with the phase transfer of Co(Ⅱ) catalyzed by 2,2′ -bipyridine across the water/nitrobenzene interface have been observed by using cyclic voltammetry (CV). Coupled chemical reactions both in the organic phase or in the aqueus phase influence the CV behavior of successive complex phase transfer obviously and an irreversible phenomenon similar to that existed at the metal electrode/electrolyte solution interface was observed. For different complexes, the phase transfer mechanism...

pCO(2) and carbon fluxes across sea-air interface in the Changjiang Estuary and Hangzhou Bay

Partial pressure of CO2 (pCO(2)) was investigated in the Changjiang (Yangtze River) Estuary, Hangzhou Bay and their adjacent areas during a cruise in August 2004, China. The data show that pCO(2) in surface waters of the studied area was higher than that in the atmosphere with only exception of a patch east of Zhoushan Archipelago. The pCO(2) varied from 168 to 2 264 mu atm, which fell in the low range compared with those of other estuaries in the world. The calculated sea-air CO2 fluxes decreased offshore and varied from -10.0 to 88.1 mmol m(-2) d(-1) in average of 24.4 +/- 16.5 mmol m(-2) d(-1). Although the area studied was estimated only 2 x 10(4) km(2), it emitted (5.9 +/- 4.0) x 10(3) tons of carbon to the atmosphere every day. The estuaries and their plumes must be further studied for better understanding the role of coastal seas playing in the global oceanic carbon cycle.

Air-Sea Exchange of Marine Trace Gases

Many of the reactive trace gases detected in the atmosphere are both emitted from and deposited to the global oceans via exchange across the air–sea interface. The resistance to transfer through both air and water phases is highly sensitive to physical drivers (waves, bubbles, films, etc.), which can either enhance or suppress the rate of diffusion. In addition to outlining the fundamental processes controlling the air–sea gas exchange, the authors discuss these drivers, describe the existing parameterizations used to predict transfer velocities, and summarize the novel techniques for measuring in situ exchange rates. They review trace gases that influence climate via radiative forcing (greenhouse gases), those that can alter the oxidative capacity of the atmosphere (nitrogen- and sulfur-containing gases), and those that impact ozone levels (organohalogens), both in the troposphere and stratosphere. They review the known biological and chemical routes of production and destruction within the water column for these gases, whether the ocean acts as a source or sink, and whether temporal and spatial variations in saturation anomalies are observed. A current estimate of the marine contribution to the total atmospheric flux of these gases, which often highlights the significance of the oceans in biogeochemical cycling of trace gases, is provided, and how air–sea gas fluxes may change in the future is briefly assessed.

Air-sea exchange of methanol and acetone during HiWinGS: Estimation of air phase, water phase gas transfer velocities

The air-sea fluxes of methanol and acetone were measured concurrently using a proton-transfer-reaction mass spectrometer (PTR-MS) with the eddy covariance (EC) technique during the High Wind Gas Exchange Study (HiWinGS) in 2013. The seawater concentrations of these compounds were also measured twice daily with the same PTR-MS coupled to a membrane inlet. Dissolved concentrations near the surface ranged from 7 to 28 nM for methanol and from 3 to 9 nM for acetone. Both gases were consistently transported from the atmosphere to the ocean as a result of their low sea surface saturations. The largest influxes were observed in regions of high atmospheric concentrations and strong winds (up to 25 m s(-1)). Comparison of the total air-sea transfer velocity of these two gases (K-a), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (k(a)) and water phase (k(w)). Among existing parameterizations, the scaling of k(a) from the COARE model is the most consistent with our observations. The k(w) we estimated is comparable to the tangential (shear driven) transfer velocity previously determined from measurements of dimethyl sulfide. Lastly, we estimate the wet deposition of methanol and acetone in our study region and evaluate the lifetimes of these compounds in the surface ocean and lower atmosphere with respect to total (dry plus wet) atmospheric deposition.

Detection of Lead Contamination of Water and VOC Contamination of Air Using SOI Micro-Optical Devices

Micro-photonic SOI Mach-Zehnder interferometers were coated with solid-phase micro-extraction materials derived from polydimethylsiloxane to enable sensing of volatile organic compounds of the BTEX class in air. A different coating based on functionalized mesoporous silicates is used to detect lead Pb(II) with a detection limit of <;; 100 ppb in water.

Platinum and Palladium in Semiconductor Photocatalytic Systems FACTORS AFFECTING THE PURIFICATION OF WATER AND AIR

A wide range of organic pollutants can be destroyed by semiconductor photocatalysis using titania. The purification of water and air contaminated with organic pollutants has been investigated by semiconductor photocatalysis for many years and in attempts to improve the purification rate platinum and palladium have been deposited, usually as fine particles, on the titania surface. Such deposits are expected to improve the rate of reduction of oxygen and so reduce the probability of electron-hole recombination and increase the overall rate of the reaction. The effectiveness of the deposits is reviewed here and appears very variable with reported rate enhancement factors ranging from 8 to 0.1. Semiconductor photocatalysis can be used to purify air (at temperatures > 100 degrees C) and Pt deposits can markedly improve the overall rate of mineralisation. However, volatile organic compounds containing an heteroatom can deactivate the photocatalyst completely and irreversibly. Factors contributing to the success of the processes are considered. The use of chloro-Pt(IV)-titania and other chloro-platinum group metals-titania complexes as possible visible light sensitisers for water and air purification is briefly reviewed.

Photocatalytic Detoxification of Water and Air

The use of semiconductor photocatalysis for treatment of water and air has been a topic of intense research activity over the past 20 years. This chapter provides a review of this highly effective technology. The fundamental processes involved in the technique are initially detailed with a discussion of some recent novel concepts in photocatalysis. A range of applications of water and air treatment are subsequently described with examples of mechanistic description of the major breakdown pathways of some key compounds. Examples of large-scale water treatment applications are also discussed.

Repeatability and reliability of new air and water permeability tests for assessing the durability of high-performance concretes

This paper reports on the accuracy of new test methods developed to measure the air and water permeability of high-performance concretes (HPCs). Five representative HPC and one normal concrete (NC) mixtures were tested to estimate both repeatability and reliability of the proposed methods. Repeatability acceptance was adjudged using values of signal-noise ratio (SNR) and discrimination ratio (DR), and reliability was investigated by comparing against standard laboratory-based test methods (i.e., the RILEM gas permeability test and BS EN water penetration test). With SNR and DR values satisfying recommended criteria, it was concluded that test repeatability error has no significant influence on results. In addition, the research confirmed strong positive relationships between the proposed test methods and existing standard permeability assessment techniques. Based on these findings, the proposed test methods show strong potential to become recognized as international methods for determining the permeability of HPCs.

Novel optical PVC probes for on-site detection/determination of fluoroquinolones in a solid/liquid interface: Application to the determination of Norfloxacin in aquaculture water

A novel optical disposable probe for screening fluoroquinolones in fish farming waters is presented, having Norfloxacin (NFX) as target compound. The colorimetric reaction takes place in the solid/liquid interface consisting of a plasticized PVC layer carrying the colorimetric reagent and the sample solution. NFX solutions dropped on top of this solid-sensory surface provided a colour change from light yellow to dark orange. Several metals were tested as colorimetric reagents and Fe(III) was selected. The main parameters affecting the obtained colour were assessed and optimised in both liquid and solid phases. The corresponding studies were conducted by visible spectrophotometry and digital image acquisition. The three coordinates of the HSL model system of the collected image (Hue, Saturation and Lightness) were obtained by simple image management (enabled in any computer). The analytical response of the optimised solid-state optical probe against concentration was tested for several mathematical transformations of the colour coordinates. Linear behaviour was observed for logarithm NFX concentration against Hue+Lightness. Under this condition, the sensor exhibited a limit of detection below 50 μM (corresponding to about 16 mg/mL). Visual inspection also enabled semi-quantitative information. The selectivity was ensured against drugs from other chemical groups than fluoroquinolones. Finally, similar procedure was used to prepare an array of sensors for NFX, consisting on different metal species. Cu(II), Mn(II) and aluminon were selected for this purpose. The sensor array was used to detect NFX in aquaculture water, without any prior sample manipulation.

Theoretical studies of the interface between water and Langmuir films of aliphatic alcohols

The interface between water and Langmuir films of long chain aliphatic molecules is investigated using accurate intermolecular potentials. The stabilities of various ice structures which could form at the interface are examined. Antiferroelectric ice is found to be the most stable, but this stability depends crucially on the first layer of water. Ferroelectric structures are found to collapse upon relaxation. Our model was not able to differentiate between the different nucleation properties of C31H63OH and C30H61OH. A better description of the alcohol–water interaction is probably required to account for this difference.