Remarkable role of positional isomers in the design of sensors for the ratiometric detection of copper and mercury ions in water

Cation sensing properties of the three positional isomers of rhodamine based sensors (1-3) are studied in water. The sensors differ only in the position of pyridine's nitrogen. The chemosensor 1, with pyridine nitrogen at ortho-position, showed a selective colorimetric detection of Cu(II) ions in water, at physiological pH 7.4 and also in medium containing BSA (bovine serum albumin) and blood serum. Notably the compound 2 and 3, with pyridine end located at meta-and para-positions did not show any color change with Cu(II) ions, although both the compounds showed turn-on change both in color and fluorescence with Hg(II) ions specifically. All the probes showed ratiometric changes with the specific metal ions. The changing position of nitrogen also changed the complexation pattern of the sensors with the metal ions. Probe 1 showed 2 : 1 complexation with Cu(II), whereas 2 and 3 showed 1 : 1 complexation with Hg(II) ions. The mechanism investigation showed that the change in color upon addition of metal ions is due to the ring-opening of the spirolactam ring of the probes. Cu(II) interacted with ligand 1 through a three-point interaction mode comprising carbonyl oxygen, amido nitrogen and pyridine nitrogen end. But in case of 2 and 3, Hg2+ only interacted through pyridine nitrogen ends. Quantitative estimation of Cu2+ and Hg2+ in complex biological media such as bovine albumin protein (BSA) and human blood serum were performed using these sensors. Rapid on-site detection as well as discrimination of these toxic ions was demonstrated using easily prepared portable test-strips.

A Probe for the Selective and Parts-per-Billion-Level Detection of Copper(II) and Mercury(II) using a Micellar Medium and Its Utility in Cell Imaging

A novel colorimetric probe 1 based on the picolyl moiety has been designed and synthesized. Probe 1 is composed of a pyrene and a bispicolyl amine (BPA) unit, in which the BPA moiety acts as a binding unit and the binding phenomenon is sensed from the changes in the signaling subunit. The probe detects Cu2+ specifically in water and both Cu2+ and Hg2+ efficiently in neutral Brij-58 micellar media. The probe shows a color change visible to the naked eye upon addition of metal ions. Notably, in a micellar medium, probe 1 can detect both the Cu2+ and Hg2+ ions even at parts-per-billion levels. Furthermore, the probe shows ratiometric detection of both the metal ions making the sensing quantitative. The two metal ions could be discriminated both visibly under a UV lamp and with the use of fluorescence spectroscopy. The probe could be also used in biological cell lines for the detection of both Hg2+ and Cu2+ ions.

Mercury exposure Aasessment in fish and humans from Sundarban Mangrove Wetland of India

Present study had documented total mercury levels in six commonly consumed fish species, and performed across-sectional study on local residents to gauge their intake of fish (via dietary survey) and mercury exposure (via hair biomarker analyses). Mean total mercury content in edible composites of locally-caught fishes (topse, hilsa, mackerel, topse, sardinella, khoira) was low and ranged from 0.01 to 0.11 mu g g(-1) mercury, dry weight. In a cross-sectional study of 58 area residents, the mercury content in hair ranged from 0.25 to 1.23 mu g g(-1), with a mean of 0.65 +/- 0.23 mu g g(-1), Flair mercury level was not influenced by gender, age, or occupation. Mean number of meals consumed per week was 3.1 +/- 1.1, and all participants consumed at least one fish meal per week. When related to fish consumption, a significant positive association was found between number of fish meals consumed per week and hair mercury levels.

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton-phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5-4.2 nm have been synthesized where emission is in the NIR region of 650-855 nm. Temperature-dependent (15-300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1-2.8 x 10(-4) eV K-1. The strength of the electron-phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17-1.68 for QDs with a size of 2.5-4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140-300 K), traps of low (13-25 meV) and high (65-140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton-acoustic phonon scattering and exciton-longitudinal optical (LO) phonon coupling. The exciton-acoustic phonon scattering coefficient is found to be enhanced up to 55 MU eV K-1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices.

Experiment on the thermocapillary convection of a mercury liquid bridge in a floating half zone

A liquid bridge of a floating half zone consisting of liquid mercury sealed in a glass tube with nitrogen atmosphere was used for the experiment of thermocapillary convection with a low Prandtl number liquid. A non-contacted diagnostic method was developed to monitor the surface flow and the surface oscillation. A growing surface film (or skin) is a crucial source to suppress thermocapillary convection, and is discussed in this paper. For the case of a mercury Liquid bridge, the critical Marangoni number was obtained as 900, and the oscillatory frequency was around 5 Hz.

Mercury in Florida Bay fish: spatial distribution of elevated concentrations and possible linkages to Everglades restoration

Health advisories are now posted in northern Florida Bay, adjacent to the Everglades, warning of high mercury concentrations in some species of gamefish. Highest concentrations of mercury in both forage fish and gamefish have been measured in the northeastern corner of Florida Bay, adjacent to the dominant freshwater inflows from the Everglades. Thirty percent of spotted seatrout (Cynoscion nebulosus Cuvier, 1830) analyzed exceeded Florida’s no consumption level of 1.5 μg g−1 mercury in this area. We hypothesized that freshwater draining the Everglades served as the major source of methylmercury entering the food web supporting gamefish. A lack of correlation between mercury concentrations and salinity did not support this hypothesis, although enhanced bioavailability of methylmercury is possible as freshwater is diluted with estuarine water. Stable isotopes of carbon, nitrogen, and sulfur were measured in fish to elucidate the shared pathways of methylmercury and nutrient elements through the food web. These data support a benthic source of both methylmercury and nutrient elements to gamefish within the eastern bay, as opposed to a dominant watershed source. Ecological characteristics of the eastern bay, including active redox cycling in near-surface sediments without excessive sulfide production are hypothesized to promote methylmercury formation and bioaccumulation in the benthos. Methylmercury may then accumulate in gamefish through a food web supported by benthic microalgae, detritus, pink shrimp (Farfantepenaeus duorarum Burkenroad, 1939), and other epibenthic feeders. Uncertainty remains as to the relative importance of watershed imports of methylmercury from the Everglades and in situ production in the bay, an uncertainty that needs resolution if the effects of Everglades restoration on mercury levels in fish are to be modeled and managed.

Foreign Aid Linked to Infrastructure and/or Pollution Abatement

This paper studies the macroeconomic effects of a permanent increase in foreign aid in a model that takes into account environmental quality. We develop a dynamic equilibrium model in which both public investment in infrastructure and environmental protection can be financed using domestic resources and international aid programs. The framework considers four scenarios for international aid: untied aid,aid fully tied to infrastructure, aid fully tied to abatement, and aid equally tied to both types of expenditures. We find that the effects of the transfers may depend on (i) the structural characteristics of the recipient country (the elasticity of substitution in production and its dependence on environment and natural resources) and on (ii) how recipient countries distribute their public expenditure. These results underscore the importance of these factors when deciding how and to what extent to tie aid to infrastructure and/or pollution abatement.

Cooperative and market-based solutions to pollution abatement problems

This work concerns itself with the possibility of solutions, both cooperative and market based, to pollution abatement problems. In particular, we are interested in pollutant emissions in Southern California and possible solutions to the abatement problems enumerated in the 1990 Clean Air Act. A tradable pollution permit program has been implemented to reduce emissions, creating property rights associated with various pollutants.

Before we discuss the performance of market-based solutions to LA's pollution woes, we consider the existence of cooperative solutions. In Chapter 2, we examine pollutant emissions as a trans boundary public bad. We show that for a class of environments in which pollution moves in a bi-directional, acyclic manner, there exists a sustainable coalition structure and associated levels of emissions. We do so via a new core concept, one more appropriate to modeling cooperative emissions agreements (and potential defection from them) than the standard definitions.

However, this leaves the question of implementing pollution abatement programs unanswered. While the existence of a cost-effective permit market equilibrium has long been understood, the implementation of such programs has been difficult. The design of Los Angeles' REgional CLean Air Incentives Market (RECLAIM) alleviated some of the implementation problems, and in part exacerbated them. For example, it created two overlapping cycles of permits and two zones of permits for different geographic regions. While these design features create a market that allows some measure of regulatory control, they establish a very difficult trading environment with the potential for inefficiency arising from the transactions costs enumerated above and the illiquidity induced by the myriad assets and relatively few participants in this market.

It was with these concerns in mind that the ACE market (Automated Credit Exchange) was designed. The ACE market utilizes an iterated combined-value call market (CV Market). Before discussing the performance of the RECLAIM program in general and the ACE mechanism in particular, we test experimentally whether a portfolio trading mechanism can overcome market illiquidity. Chapter 3 experimentally demonstrates the ability of a portfolio trading mechanism to overcome portfolio rebalancing problems, thereby inducing sufficient liquidity for markets to fully equilibrate.

With experimental evidence in hand, we consider the CV Market's performance in the real world. We find that as the allocation of permits reduces to the level of historical emissions, prices are increasing. As of April of this year, prices are roughly equal to the cost of the Best Available Control Technology (BACT). This took longer than expected, due both to tendencies to mis-report emissions under the old regime, and abatement technology advances encouraged by the program. Vve also find that the ACE market provides liquidity where needed to encourage long-term planning on behalf of polluting facilities.

I. A recirculating charged-couple device. II. The mercury selenide on N-silicon Schottky barrier

A recirculating charge-coupled device structure has been devised. Entrance and exit gates allow a signal to be admitted, recirculated a given number of times, and then examined. In this way a small device permits simulation of a very long shift register without passing the signal through input and output diffusions. An oscilloscope motion picture demonstrating degradation of an actual circulating signal has been made. The performance of the device in simulating degradation of a signal by a very long shift register is well fit by a simple model based on transfer inefficiency.

Electrical properties of the mercury selenide on n-type chemically-cleaned silicon Schottky barrier have been studied. Barrier heights measured were 0.96 volts for the photoresponse technique and 0.90 volts for the current-voltage technique. These are the highest barriers yet reported on n-type silicon.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Metallothionein as an indicator of water quality: assessment of the bioavailability of cadmium, copper, mercury and zinc in aquatic animals at the cellular level

The study of metallothioneins (MTs) has greatly improved our understanding of body burdens, metal storage and detoxification in aquatic organisms subjected to contamination by the toxic heavy metals, Cd, Cu, Hg and Zn. These studies have shown that in certain organisms MT status can be used to assess impact of these metals at the cellular level and, whilst validation is currently limited to a few examples, this stress response may be linked to higher levels of organisation, thus indicating its potential for environmental quality assessment. Molluscs, such as Mytilus spp., and several commonly occurring teleost species, are the most promising of the indicator species tested. Natural variability of MT levels caused by the organism's size, condition, age, position in the sexual cycle, temperature and various stressors, can lead to difficulties in interpretation of field data as a definitive response-indicator of metal contamination unless a critical appraisal of these variables is available. From laboratory and field studies these data are almost complete for teleost fish. Whilst for molluscs much of this information is lacking, when suitable controls are utilised and MT measurements are combined with observations of metal partitioning, current studies indicate that they are nevertheless a powerful tool in the interpretation of impact, and may prove useful in water quality assessment.

Responses of plasma transaminase activity in Cyprinus carpio var. communis to mercury toxicity

The present study reports the behavioural and enzymological responses in a freshwater teleost fish, Cyprinus carpio var. communis, exposed to acute and sublethal toxicities of mercuric chloride. During acute treatment, significant behavioural changes like erratic swimming, excess mucus secretion and increased opercular movements were noticed. During acute and sublethal treatments, both aspartate amino transferase and alanine amino transferase activity increased throughout the study period. Comparing the treatments, the changes in enzyme activities were found high in acute treatment and all the values were significant at 5% level. The above findings can be used as non-specific biomarkers of environmental pollutants.