Air Pollution in Singapore: Its Multielemental Aspect as Measured by Nuclear Analytical Techniques

Aerosol samples were collected in 1994 in Singapore on two occasions: once in June during the normal meteorological conditions and later in October during a long haze period caused by the heavy forest fire in Indonesia. Filtration and impaction collection methods were used simultaneously so that detailed elemental analysis of bulk as well as of different size fractions could be performed. Accelerator based nuclear analytical techniques such as Particle Induced X-Ray Emission (PIXE), Rutherford Backscattering (RBS) and Nuclear Microscopy (NM) were used for analysis. These techniques are fast, truly multielemental and perfectly suited for routine analysis of a large number of aerosol samples. Typically all samples were analysed for the following 24 elements: Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Mn, Cr, Fe, Co, Ni, Cu, Zn, Ga, As, Br, Rb, Sr and Pb. Detection limits for bulk analysis were generally below ng/m3 and for single particle analysis absolute detectable mass was approximately 10-17 g. Additionally, trace elements such as Cd, Sn, Sb and Ba whose characteristic X-ray lines were normally "obscured" by the lines of other more abundant elements, were detected when analysing by nuclear microscope in single particle mode.Judging by the average concentrations of lead and sulphur which are good indicators of industrial component of air pollution the situation in Singapore is satisfactory. Pb was typically found in concentrations of 5 to 50 ng/m3 and sulphur in concentrations of 1 to 2 µg/m3. These concentrations are well below limits set by the World Health Organisation (1500 ng/m3 and 40 µg/m3, respectively). On the other hand during the haze period the average concentrations of elements like S, K, Ti, V, Mn, Ni, As and Pb were found to be 3 to 6 times higher than usual. Results are presented and discussed.     

Recycling of petroleum-contaminated sand

The environmental impact of using petroleum-contaminated sand (PCS) as a substitute in asphalt paving mixtures was examined. An appreciable component of PCS is oily sludge, which is found as the dregs in oil storage tanks and is also produced as a result of oil spills on clean sand. The current method for the disposal of oily sludge is land farming. However, this method has not been successful as an oil content of < 1% w/w is required, and difficulty was encountered in reaching this target. The reuse of the sludge in asphalt paving mixtures was therefore considered as an alternative. Standard tests and environmental studies were conducted to establish the integrity of the materials containing the recycled sludge. These included physical and chemical characterization of the sludge itself, and an assessment of the mechanical properties of materials containing 0%, 5%, 22% and 50% oily sludge. The blended mixtures were subjected to special tests, such as Marshall testing and the determination of stability and flow properties. The experimental results indicated that mixtures containing up to 22% oily sludge could meet the necessary criteria for a specific asphalt concrete wearing course or bituminous base course. To maximize the assay from the recycled material, the environmental assessment was restricted to the 50% oily sludge mixture. Leachates associated with this particular mixture were assayed for total organic residue and certain hazardous metal contaminants. The results revealed that the organics were negligible, and the concentrations of the metals were not significant. Thus, no adverse environmental impact should be anticipated from the use of the recycled product. Our research showed that the disposal of oily sludge in asphalt paving mixtures could possibly yield considerable savings per tonne of asphalt concrete, and concurrently minimize any direct impact on the environment.     

Concentration and Distribution of Persistent Organic Pollutants (POPs) in Harbour Dredging Sediments: A Pilot Study Using a Statistical Approach for a More Efficient Characterisation and Management

The Italian guidelines concerning the dumping of dredgingmaterials implies chemical, physical and microbiologicalcharacterisation of dumping sediments collected through aspecific sampling strategy.POP's such as PCB's and organochlorine pesticides, areconsidered as priority pollutants in all the InternationalConventions for the protection of the marine environment, inconsequence of their persistence, toxicity and bioaccumulation capacity.In the present article the concentrations and distribution ofPCB's and organochlorine pesticides in dredging sediments ofPiombino harbour (northern Thyrrenian sea) were investigates.The results showed high POP's concentrations in all the studiedareas. The maximum values were: 3.94 mg kg^-1 dry weight for PCB's(IUPAC Nos. 28; 52; 101, 118; 137; 153; 180; 209); 2.04 mg kg^-1 d.w.for HCH's (-, -, - and -hexachlorocyclohexane isomers); 0.28 mg kg^-1 d.w. for DD's (DDT + DDE + DDD).Subsequently, the data related to each pollutant were treatedwith statistical tests, in order to verify how well the samplingstrategy is able to represent the distribution of contaminantsin the dredging area. Finally, management strategies werederived for the studied dredging sediments.     

Chlorinated Hydrocarbons in Livers of American Mink (Mustela vison) and River Otter (Lutra canadensis) from the Columbia and Fraser River Basins, 1990–1992

We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990–91 and 1991–92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 g/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978–79 and 1990–92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 g/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.     

State estimation in wastewater engineering: Application to an anaerobic process

The use of an extended Kalman filter for state estimation in biological wastewater treatment processes is discussed. The application of the technique requires an adequate mechanistic dynamic model and the identification and modelling of the major sources of stochastic disturbances in the process. The filter allows the on-line tracking of process variables which are not directly measurable. The use of an extended Kalman filter is illustrated through a simulated application to a high rate anaerobic wastewater treatment process.     

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Impact of automobile emissions on the levels of platinum and lead in Accra,Ghana

Examination of car fleet records in Accra demonstrates an increasing proportion of catalytic converter-equipped cars in the relatively old car fleet (average age 13 years) due to their import from developed countries. However, only leaded petrol is sold in Ghana. Lead anti-knocking additives, which are known to affect catalyst activity and promote thermal sintering and mechanical abrasion, may increase Pt emissions. This possible synergism prompted the concomitant determination of Pb and Pt levels in road dust and roadside soils in Ghana. Both metals followed traffic density with higher concentrations in urban areas compared to remote sites. In urban areas, the range for Pb (365 +/- 93 microg g(-1) for dust and 291 +/- 76 microg g(-1) for soil) reflects precatalyst levels in Europe and the US, while the range for Pt (39 +/- 24 ng g(-1) for dust and 15 +/- 5.3 ng g(-1) for soil) is typical for the same countries. The elevated Pt concentrations were unexpected due to recent introduction of catalysts to Ghana compared to the prolonged use of catalysts in Europe and the US.     

Suspended particulates and bioaerosols emitted from an agricultural non-point source

Suspended particulate and bioaerosol levels were measured at three sites downwind of an agricultural non-point source during the wheat harvesting season. Suspended particulates were detected at mean values ranging from 10000 to 2420 micrograms m-3 at distances of from 20 to 60 m downwind of the source, respectively. Airborne viable bacterial counts were recorded at mean values ranging between 10(4) and 10(6) colony forming units (cfu) m-3, whereas, Gram negative (Gram -ve) bacteria varied between 10(3) and 10(5) cfu m-3. Fungi levels were detected at mean values varying between 10(5) and 10(6) cfu m-3. However, streptomycetes were found at lower counts than those recorded for viable bacteria and fungi. Total viable bacteria, Gram -ve bacteria, fungi and streptomycetes associated hay fragments were determined at mean values of 1.5 x 10(6), 1.6 x 10(3), 2.2 x 10(4) and 6 x 10(3) cfu g-1 of hay, respectively. Cladosporium, white and red yeasts as well as Alternaria were the predominant airborne fungi, whereas, Alternaria was the dominant species associated with hay fragments. Pseudomonas, Acinetobacter and Enterobacteriaceae were the dominant Gram -ve bacteria. The most common fungal genera, such as Cladosporium and Fusarium (minor short axis), as well as Streptomyces species have an aerodynamic diameter (dae) of less than 5 microns, which can penetrate and deposit in the alveoli. Farmers and nearby residents are exposed to high levels of organic dust and bioaerosols during the wheat harvesting season. This may cause health problems in exposed persons based on toxic or allergic reactions.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).