Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Microwave-Assisted Solvent Extraction of Air Particulates for the Determination of PAHs

A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in air particulates using microwave-assisted solvent extraction (MASE) coupled to a microwave extraction system (MES) is proposed. During the period of August to October, 1994, Singapore was enveloped by haze caused by forest fires in Sumatra, Indonesia. Air sampling were carried out during September and October; the determination of ambient air PAH levels in Singapore was undertaken. PAH analysis by GC-MS provided excellent sensitivity, linearity of quantitation, peak identification. This technique was evaluated using certified reference materials (CRMs) HS-4 and HS-6. Good recoveries of PAHs (>73.3%) were obtained for both CRMs. The MASE technique using MES is suitable for the determination of PAH levels in ambient air with no clean-up step required.     

evaluation of a measurement method for forest vegetation in a large-scale ecological survey

We evaluate a field method for determining species richness andcanopy cover of vascular plants for the Forest Health MonitoringProgram (FHM), an ecological survey of U.S. forests. Measurementsare taken within 12 1-m² quadrats on 1/15 ha plots in FHM.Species richness and cover are determined for four height classes(strata) within each quadrat and aggregated by stratum over the entireplot. We estimated (1) the agreement between experienced trainers andinexperienced technicians who collected the data on this survey(accuracy) and (2) the agreement among the technicians (precision) forresults on species richness and cover from 3 test plots at 3 timeintervals. The methods appear to be highly precise, although somediscrepancies with the values obtained by the trainers were found.Trainers found significantly more species in the ground stratum (0–0.6 m) and measured significantly more cover in the uppermost stratum(>4.9 m). The proportion of variation due to measurement error andtemporal variability was less than 13% for species richness (all strata)and cover (all but one stratum). This indicates that the method issuitable for monitoring changes in species richness and canopy coverfor a large-scale synoptic monitoring project such as FHM.     

Chemical and Bacteriological Monitoring of Drinking Water from an Urbanised Water Catchment Drainage Basin

The Linggi river drainage basin in Negeri Sembilan, Malaysia supplies water to the whole of Port Dickson district and meets 50% of the Seremban district needs. The Linggi River, the main tributary, passes through the highly urbanised and densely populated Seremban district while the water treatment plant is located 16 km downstream. In 1979 the USEPA declared the river unsuitable as a source of raw water whereas the WHO classified it as being heavily polluted requiring more extensive and effective treatment. In order to meet the WHO drinking water standards, an ozonation system was installed in the conventional water treatment plant. The objective of ozonation is for the control and removal of organic micropollutants and other deleterious matters. This study investigated the concentrations and distribution of organic micropollutants, heavy metals, and bacteriological counts in water samples collected from within the catchment and the treated water. The effectiveness of the ozonation system was also studied. The total level of phenolic water pollutants in the catchment was generally found to be very much higher than the maximum recommended level of 2.0 µgl-1. The extensive treatment process carried out at the plant was very effective in reducing the levels of total phenols in the treated water to less than 1.0 µgl-1. However the process was not efficient enough to reduce the levels of some heavy metals as required by the standards, for examples Cd and Pb were still three times higher than the standards of 5µgl-1 and 0.05 mgl-1 respectively. For bacteriological study, coliform group of bacteria, Salmonella, faecal streptococci and injured coliform were monitored in the raw and treated water. The raw water contained coliforms about 1000 times higher than the required standard for raw ater, but after the secondary treatment by ozonation coliform bacteria were absent, however a small number of Salmonella was still present occasionally. The study also showed that restructuring of the district and relocating of some commercial activities along the river banks to other areas carried out over the last five years has improved the general quality of the river water.     

Soil Lead and Other Metal Levels in Industrial, Residential and Nature Reserve Areas in Singapore

The use of pressure feedback microwave digestion technique has permitted rapid and efficient digestion of soil and sediment samples. The evaluation of different acid mixtures to digest soil samples were studied by mixed-level orthogonal array design. The selected acid mixture of HCl-HNO3-HF was employed in the survey of Pb, Zn, Cu, Cr and Mn in soil samples. Surface soil samples were collected from industrial, residential and nature reserve areas in Singapore. The five metal concentrations were determined by flame atomic absorption spectrometry and graphite furnace atomic absorption spectrometry. The lead and other metal contents in NBS SRM 1645, NIES CRM No. 2 and NRCC BCSS-1 sediment standard references were determined concurrently with the survey samples. Five measured metal loading on the surface soils was in the order: industrial area > residential area > nature reserve area. The trace metal concentrations in surface soil from areas of heavy traffic are higher than those from residential areas. The main sources of trace metal pollution are vehicular exhaust and industrial activities.     

A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

RISK ASSESSMENT METHODOLOGY FOR KARST AQUIFERS: (2) SOLUTE-TRANSPORT MODELING

Ground-water flow and solute-transport simulation modeling are major components of most exposure and risk assessments of contaminated aquifers. Model simulations provide information on the spatial and temporal distributions of contaminants in subsurface media but are difficult to apply to karst aquifers in which conduit flow is important. Ground-water flow and solute transport in karst conduits typically display rapid-flow velocities, turbulent-flow regimes, concentrated pollutant-mass discharge, and exhibit open-channel or closed-conduit flow. Conventional ground-water models, dependent on the applicability of Darcy`s law, are inappropriate when applied to karst aquifers because of the (1) nonapplicability of Darcian-flow parameters, (2) typically nonlaminar flow regime, and (3) inability to locate the karst conduits through which most flow and contaminant transport occurs. Surface-water flow and solute-transport models conditioned on a set of parameters determined empirically from quantitative ground-water tracing studies may be effectively used to render fate-and-transport values of contaminants in karst conduits. Hydraulic-flow and geometric parameters developed in a companion paper were used in the surface-water model, TOXI5, to simulate hypothetical slug and continuous-source releases of ethylbenzene in a karst conduit. TOXI5 simulation results showed considerable improvement for predicted ethylbenzene-transport rates and concentrations over qualitative tracing and analytical ground-water model results. Ethylbenzene concentrations predicted by TOXI5 simulations were evaluated in exposure and risk assessment models.     

Optimal charges on river effluent from lumped and distributed sources

We propose a modelling framework for the design of a Pigouvian effluent tax, in an environmental management problem implicating several economic agents located in a river basin. The proposed charging system allows for the agents' geographical position relative to the river's sections, at which environmental standards are to be enforced, and takes into account the possible different market structures within which the agents are operating. In particular, we consider industrial agents competing on an oligopolistic market, and a set of farmers acting as price takers on a large market. A regional authority's goal is to induce agents to some sort of cooperation which would result in the satisfaction of the common environmental constraints. The economic process on one side, and the pollution transport and accumulation on the other, constitute two dynamic processes in two different time scales. As the economic process is much slower than the other process we can neglect the latter's transients and concentrate on the time invariant steady state solutions to the transportation equation. The model thus constructed has some noncooperative game and optimal control problem's features with space being the ‘running’ variable. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of Meteorological Aspects and Urban Concentration of SO2 in Atmospheric Environment of La Plata, Argentina

This article presents and discusses SO₂ (ppbv) concentration measurements combined with meteorological data (mainly wind speed and direction) for a five-year campaign (1996 to 2000), in a site near an oil refinery plant close to the city of La Plata and surroundings (aprox. 740.000 inh.), considered one of the six most affected cities by air pollution in the country. Since there is no monitoring network in the area, the obtained results should be considered as medium term accumulated data that enables to determine trends by analyzing together gas concentrations and meteorological parameters. Preliminary characterization of the behaviour of the predominant winds of the region in relation with potential atmospheric gas pollutants from seasonal wind roses is possible to carry out from the data. These results are complemented with monthly averaged SO₂ measurements. In particular, for year 2000, pollutant roses were determined which enable predictions about contamination emission sources. As a general result we can state that there is a clear increase in annual SO₂ concentration and that the selected site should be considered as a key site for future survey monitoring network deployment. Annual SO₂ average concentration and prevailing seasonal winds determined in this work, together with the potential health impact of SO₂ reveals the need for a comprehensive and systematic study involving particulate matter an other basic pollutant gases.