Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

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).     

Microbiological characteristics in a zero-valent iron reactive barrier

Zero-valent iron (Fe⁰)-based permeable reactive barriertreatment has been generating great interest for passivegroundwater remediation, yet few studies have paid particularattention to the microbial activity and characteristics withinand in the vicinity of the Fe⁰-barrier matrix. The presentstudy was undertaken to evaluate the microbial population andcommunity composition in the reducing zone of influence byFe⁰ corrosion in the barrier at the Oak Ridge Y-12 Plantsite. Both phospholipid fatty acids and DNA analyses were usedto determine the total microbial population and microbialfunctional groups, including sulfate-reducing bacteria,denitrifying bacteria, and methanogens, in groundwater andsoil/iron core samples. A diverse microbial community wasidentified in the strongly reducing Fe⁰ environment despitea relatively high pH condition within the Fe⁰ barrier (up topH 10). In comparison with those found in the backgroundsoil/groundwater samples, the enhanced microbial populationranged from 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. Inaddition, microbial community composition appeared to change overtime, and the bacterial types of microorganismsincreased consistently as the barrier aged. DNA analysisindicated the presence of sulfate-reducing and denitrifyingbacteria in the barrier and its surrounding soil. However, theactivity of methanogens was found to be relatively low,presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidenceof a diverse microbial population within and in the vicinity ofthe iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevityand enduring efficiency of the Fe⁰ barriers are yet to be evaluated.     

Multi-objective, decision-based assessment of a water quality monitoring network in a river system

Water quality monitoring network design has historically tended to use experience, intuition and subjective judgement in locating monitoring stations. Better design procedures to optimize monitoring systems need to simultaneously identify significant planning objectives and consider a number of social, economic and environmental constraints. The consideration of multiple objectives may require further decision analysis to determine the preference weights associated with the objectives to aid in the decision-making process. This may require the application of an optimization study to extract such information from decision makers or experts and to evaluate the overall effectiveness of locating strategies. This paper assesses the optimal expansion and relocation strategies of a water quality monitoring network using a two-stage analysis. The first stage focuses on the information retrieval of preference weights with respect to the designated planning objectives. With the aid of a pre-emptive goal programming model, data analysis is applied to obtain the essential information from the questionnaire outputs. The second stage then utilizes a weighted multi-objective optimization approach to search for the optimal locating strategies of the monitoring stations in the river basin. Practical implementation is illustrated by a case study in the Kao-Ping River Basin, south Taiwan.     

Applying mathematical programming to reserve selection

During the last 10–15 years heuristic methods have been developed for problems in optimal reserve selection. Unfortunately, there is no guarantee that heuristics will find optimal solutions. In recognizing this limitation, analysts have formulated reserve selection problems as set covering problems, for which matrix reduction and integer (0/1) programming can be used to find optimal solutions. In this paper we restate the set covering formulation and review solution techniques. A new 0/1 programming model, which is a generalization of the set covering model, is then presented and applied to a hypothetical reserve selection problem. Objectives of minimizing the number of sites selected and maximizing the number of species represented are addressed. Solutions which characterize the tradeoffs between these objectives provide a rich set of information for planners and decision makers. Applications of mathematical programming to related problems in land use planning and forestry are also discussed.     

Optimal and suboptimal control of anaerobic digesters

Anaerobic digester failure due to entry of inhibitors or sudden changes in the feed substrate concentration may be encompassed beneficially by applying optimal control theory. An almost proportional relationship between the dilution rate and the methane production rate leads to a simple suboptimal control law with only minor loss in performance, after the occurrence of the above mentioned events.     

Reduction of SO2 emissions by ammonia gas during unstaged combustion

The reduction of SO₂ by the addition of ammonia gas has been studied in a 2 m high fluidized bed combustor having a 30 cm static bed height and a freeboard height of 170 cm. Ammonia gas was injected at 52 cm above the distributor where the temperature is ca. 700° C by an uncooled stainless steel tube injector. Experiments were carried out to investigate the effects of amminia gas injection on sulphur dioxide emissions at unstaged conditions of: (i) excess air level, (ii) NH₃:SO₂ molar ratio, (iii) fluidizing velocity and (iv) bed height.A maximum reduction of 75% in SO₂ emissions was found at 40% excess air, at an NH₃:SO₂ molar ratio of 5.4. The onset of SO₂ reduction occurred at an NH₃:SO₂ ratio of 1.5 However, the most effective ratio was found to be between 3 and 5. Fluidizing velocity and bed height were also found to have significant influence on SO₂ reduction.It is difficult to determine how the SO₂ reduction varied with operating conditions. When ammonia is added in the main combustor zone, the temperature is much higher than that required for the occurrence of sulphur dioxide-ammonia and sulphur trioxide-ammonia reactions. However, this paper points out the significance of ammonia addition in the reduction of sulphur dioxide.     

The analysis of monitoring data with the aid of time-series analysis

Methods derived from time-series analysis are proposed for processing monitoring data. The necessity for the use of these methods is demonstrated. In a case study time-series analysis was applied to assess the impact of the closure of the Grevelingen estuary (S. W. Netherlands) in 1971 on a local wintering population of Oystercatchers (Haematopus ostralegus) in the adjacent Oosterschelde estuary.Communication No. 328 of the Delta Institute for Hydrobiological Research.