Mobile monitoring along a street canyon and stationary forest air monitoring of formaldehyde by means of a micro-gas analysis system

A micro-gas analysis system (μGAS) was developed for mobile monitoring and continuous measurements of atmospheric HCHO. HCHO gas was trapped into an absorbing/reaction solution continuously using a microchannel scrubber in which the microchannels were patterned in a honeycomb structure to form a wide absorbing area with a thin absorbing solution layer. Fluorescence was monitored after reaction of the collected HCHO with 2,4-pentanedione (PD) in the presence of acetic acid/ammonium acetate. The system was portable, battery-driven, highly sensitive (limit of detection = 0.01 ppbv) and had good time resolution (response time 50 s). The results revealed that the PD chemistry was subject to interference from O(3). The mechanism of this interference was investigated and the problem was addressed by incorporating a wet denuder. Mobile monitoring was performed along traffic roads, and elevated HCHO levels in a street canyon were evident upon mapping of the obtained data. The system was also applied to stationary monitoring in a forest in which HCHO formed naturally via reaction of biogenic compounds with oxidants. Concentrations of a few ppbv-HCHO and several-tens of ppbv of O(3) were then simultaneously monitored with the μGAS in forest air monitoring campaigns. The obtained 1 h average data were compared with those obtained by 1 h impinger collection and offsite GC-MS analysis after derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA). From the obtained data in the forest, daily variations of chemical HCHO production and loss are discussed.     

Removal of uranium(VI) from contaminated sediments by surfactants

Uranium(VI) sorption onto a soil collected at the Melton Branch Watershed (Oak Ridge National Laboratory, TN) is strongly influenced by the pH of the soil solution and, to a lesser extent, by the presence of calcium, suggesting specific chemical interactions between U(VI) and the soil matrix. Batch experiments designed to evaluate factors controlling desorption indicate that two anionic surfactants, AOK and T77, at concentrations ranging from 60 to 200 mM, are most suitable for U(VI) removal from acidic soils such as the Oak Ridge sediment. These surfactants are very efficient solubilizing agents at low uranium concentrations: ca. 100% U(VI) removal for [U(VI)]o,sorbed = 10(-6) mol kg-1. At greater uranium concentrations (e.g., [U(VI)]o,sorbed = ca. 10(-5) mol kg-1), the desorption efficiency of the surfactant solutions increases with an increase in surfactant concentration and reaches a plateau of 75 to 80% of the U(VI) initially sorbed. The most probable mechanisms responsible for U(VI) desorption include cation exchange in the electric double layer surrounding the micelles and, to a lesser extent, dissolution of the soil matrix. Limitations associated with the surfactant treatment include loss of surfactants onto the soil (sorption) and greater affinity between U(VI) and the soil matrix at large soil to liquid ratios. Parallel experiments with H2SO4 and carbonate-bicarbonate (CB) solutions indicate that these more conventional methods suffer from strong matrix dissolution with the acid and reduced desorption efficiency with CB due to the buffering capacity of the acidic soil.     

Photochemical decomposition of environmentally persistent short-chain perfluorocarboxylic acids in water mediated by iron(II)/(III) redox reactions

The photochemical decomposition of short-chain (C(3)-C(5)) perfluorocarboxylic acids (PFCAs) was investigated. Direct photolysis in water proceeded slowly with the 220- to 460-nm light emission from a xenon-mercury lamp to form F(-), CO(2), and shorter-chain PFCAs. Addition of a small amount of Fe(3+) to the aqueous solutions of the PFCAs dramatically enhanced their photochemical decomposition under an oxygen atmosphere: when the (initial PFCA)/(initial Fe(3+)) molar ratio was 13.5 (initial PFCA concentration=67.3mM), the pseudo-first-order rate constants for the PFCA decomposition were 3.6-5.3 times those with photolysis alone, and the turnover number for the catalytic PFCA decomposition [i.e., (moles of decomposed PFCA)/(moles of initial Fe(3+))] reached 6.71-8.68 after 24h of irradiation. The catalysis can be explained by photoredox reactions between PFCA, Fe(3+)/Fe(2+) and oxygen via photo-induced complexation of Fe(3+) with the PFCAs.     

Effect of arsenic-contaminated irrigation water on agricultural land soil and plants in West Bengal, India

Total arsenic withdrawn by the four shallow tubewells, used for agricultural irrigation in the arsenic-affected areas of Murshidabad district per year is 6.79 kg (mean: 1.79 kg, range: 0.56-3.53 kg) and the mean arsenic deposition on land per year is 5.02 kg ha(-1) (range: 2-9.81 kg ha(-1)). Mean soil arsenic concentrations in surface, root of plants, below ground level (0-30 cm) and all the soils, collected from four agricultural lands are 14.2 mg/kg (range: 9.5-19.4 mg/kg, n = 99), 13.7 mg/kg (range: 7.56-20.7 mg/kg, n = 99), 14.8 mg/kg (range: 8.69-21 mg/kg, n = 102) and 14.2 mg/kg (range: 7.56-21 mg/kg, n = 300) respectively. Higher the arsenic in groundwater, higher the arsenic in agricultural land soil and plants has been observed. Mean arsenic concentrations in root, stem, leaf and all parts of plants are 996 ng/g (range: <0.04-4850 ng/g, n = 99), 297 ng/g (range: <0.04-2900 ng/g, n = 99), 246 ng/g (range: <0.04-1600 ng/g, n = 99) and 513 ng/g (range: <0.04-4850 ng/g, n = 297) respectively. Approximately 3.1-13.1, 0.54-4.08 and 0.36-3.45% of arsenic is taken up by the root, stem and leaf respectively, from the soil.     

Arsenic and other heavy metals in soils from an arsenic-affected area of West Bengal,India

Domkal is one of the 19, out of 26 blocks in Murshidabad district where groundwater contains arsenic above 0.05 mg/l. Many millions of cubic meters of groundwater along with arsenic and other heavy metals are coming out from both the hand tubewells, used by the villagers for their daily needs and shallow big diameter tubewells, installed for agricultural irrigation and depositing on soil throughout the year. So there is a possibility of soil contamination which can moreover affect the food chain, cultivated in this area. A somewhat detailed study was carried out, in both micro- and macrolevel, to get an idea about the magnitude of soil contamination in this area. The mean concentrations (mg/kg) of As (5.31), Fe (6740), Cu (18.3), Pb (10.4), Ni (18.8), Mn (342), Zn (44.3), Se (0.53), Mg (534), V (44.6), Cr (33.1), Cd (0.37), Sb (0.29) and Hg (0.54) in fallow land soils are within the normal range. The mean As (10.7), Fe (7860) and Mg (733) concentrations (mg/kg) are only in higher side whereas Hg (0.17 mg/kg) is in lower side in agricultural land soils, compared to the fallow land soils. Arsenic concentrations (11.5 and 28.0 mg/kg respectively) are high in those agricultural land soils where irrigated groundwater contains high arsenic (0.082 and 0.17 mg/l respectively). The total arsenic withdrawn and mean arsenic deposition per land by the 19 shallow tubewells per year are 43.9 kg (mean: 2.31 kg, range: 0.53-5.88 kg) and 8.04 kg ha(-1) (range: 1.66-16.8 kg ha(-1)) respectively. For the macrolevel study, soil arsenic concentration decreases with increase of distance from the source and higher the water arsenic concentration, higher the soil arsenic at any distance. A proper watershed management is urgently required to save the contamination.     

Sorption of arsenate and arsenite anions by iron(III)-poly(hydroxamic acid) complex

Iron(III)-poly(hydroxamic acid) resin complex has been studied for its sorption abilities with respect to arsenate and arsenite anions from an aqueous solution. The complex was found effective in removing the arsenate anion in the pH range of 2.0 to 5.5. The maximum sorption capacity was found to be 1.15 mmol/g. The sorption selectivity showed that arsenate sorption was not affected by chloride, nitrate and sulphate. The resin was tested and found effective for removal of arsenic ions from industrial wastewater samples.     

Particle Surface Hydrophobicity and the Dechlorination of Chloro-Compounds by Iron Sulfides

Halogenated aliphatic compounds (HACs) can be reduced by iron sulfides in aqueous systems. Generally, the thermodynamics and kinetics of dehalogenation reactions are controlled by the mineralogical and particle surface characteristics of the iron sulfide, the composition of the HAC and reaction conditions such as component concentrations, pH and Eh. In this theoretical and experimental investigation of CCl₄ and C₂Cl₆ reduction by FeS and FeS₂, the roles of hydrophobic and hydrophilic sites on the iron sulfides were analyzed. Experimental data obtained through zeta potential measurements, were used along with the Gouy-Chapman model and the simple two-layer surface complexation model to relate iron sulfide surface hydroxyl densities to the degree of HAC dehalogenation. The surface hydroxyl site densities of FeS and FeS₂ were found to be 0.11 sites/nm² and 0.21 sites/nm², respectively. During the dehalogenation reaction process, CCl₄ was found to decrease to its first intermediate product CHCl₃ within the first 20 hours followed by a slower process of conversion to CH₂Cl₂. The results also show that FeS is less hydrated (more hydrophobic) than FeS₂. For CCl₄ and C₂Cl₆, FeS is a better dehalogenator than FeS₂. These results imply that particle surface hydrophobicity is a critical factor in surface-mediated dehalogenation of chlorinated compounds.     

Extraction of arsenic in a synthetic arsenic-contaminated soil using phosphate

An environment-friendly and cost-effective extraction method has been studied for the removal of arsenic from contaminated soil. A yellow-brown forest soil was contaminated with arsenic(V) and used as a model soil. Among various potassium and sodium salts, potassium phosphate was most effective in extracting arsenic, attaining more than 40% extraction in the pH range of 6–8 with minimum damage to the soil properties. Exchange mechanism is proposed for the extraction of arsenic from soil by phosphate. Sequential extraction shows that phosphate is effective in extracting arsenic of Al- and Fe-bound forms. Arsenic of residual form was not extracted. Arsenic was efficiently extracted by phosphate solution of pH 6.0 at 300 mM phosphate concentration and at 40°C.     

Photocatalytic mineralization of hydroperfluorocarboxylic acids with heteropolyacid H₄SiW₁₂O₄₀ in water

The decomposition of hydroperfluorocarboxylic acids [H-PFCAs; HC_nF_2nCOOH (n = 4 and 6)] induced by heteropolyacid photocatalyst H₄SiW₁₂O₄₀ in water was investigated, and the results are compared with the results for the corresponding perfluorocarboxylic acids (PFCAs; C_nF_2n+1COOH). This is the first report on the photochemical decomposition of H-PFCAs, which are being developed as alternative surfactants to environmentally persistent and bioaccumulative PFCAs. H-PFCAs were not decomposed by irradiation with UV-Visible light (>290 nm) in the absence of H₄SiW₁₂O₄₀. In contrast, UV-Visible light irradiation of H-PFCAs in the presence of H₄SiW₁₂O₄₀ efficiently decomposed H-PFCAs to F⁻ and CO₂. The decomposition reactions showed pseudo-first-order kinetics, and the decomposition rate constants were 1.8-2.5 times higher than those for the corresponding PFCAs. The reaction mechanism can be explained by elimination of H⁺ from the ω-H atom of the H-PFCAs by the excited catalyst, followed by formation of perfluorodicarboxylic acids.     

Sediment tolerance of Sargassum algae inhabiting sediment-covered rocky reefs

Although sediment deposition has detrimental effects on macroalgal settlement and recruitment, fucoid algae (mainly Sargassum duplicatum) thrive on rocky reefs always overlaid with fine sediments in sheltered sites of Kagoshima, Japan. The aim of the present study was to assess their ability to settle and recruit onto sediment-covered substrata. A transplant experiment using boulders with Sargassum juveniles attached showed that the 30-day survival rate was as high as 50% even for the juvenile stage (<10 mm) on boulders completely buried with sediment. In addition, an outdoor tank experiment testing the effects of different sediment thicknesses (0–4 mm) on already settled 4-day old S. duplicatum germlings indicated significant reductions in growth by the presence of sediment cover even at 0.5 mm but no significant increase in mortality up to 2 mm. Furthermore, an in situ experiment in which sterilized cobbles were placed at a sediment-covered site to allow sediment to settle over them before the embryo release showed a uniformly high recruitment of Sargassum over the cobbles. This suggests the presence of unknown mechanisms to allow the settlement of propagules on substrata thinly but completely covered by fine sediments.