Effects of copper(II) and copper oxides on THMs formation in copper pipe

Little is known about how the growth of trihalomethanes (THMs) in drinking water is affected in copper pipe. The formation of THMs and chlorine consumption in copper pipe under stagnant flow conditions were investigated. Experiments for the same water held in glass bottles were performed for comparison. Results showed that although THMs levels firstly increased in the presence of chlorine in copper pipe, faster decay of chlorine as compared to the glass bottle affected the rate of THMs formation. The analysis of water phase was supplemented by surface analysis of corrosion scales using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDX). The results showed the scales on the pipe surface mainly consisted of Cu₂O, CuO and Cu(OH)₂ or CuCO₃. Designed experiments confirmed that the fast depletion of chlorine in copper pipe was mainly due to effect of Cu₂O, CuO in corrosion scales on copper pipe. Although copper(II) and copper oxides showed effect on THMs formation, the rapid consumption of chlorine due to copper oxide made THM levels lower than that in glass bottles after 4 h. The transformations of CF, DCBM and CDBM to BF were accelerated in the presence of copper(II), cupric oxide and cuprous oxide. The effect of pH on THMs formation was influenced by effect of pH on corrosion of copper pipe. When pH was below 7, THMs levels in copper pipe was higher as compared to glass bottle, but lower when pH was above 7.     

PAHs in the bulk atmospheric deposition of the Seine river basin: source identification and apportionment by ratios, multivariate statistical techniques and scanning electron microscopy

The origin of polycyclic aromatic hydrocarbons (PAH) contamination in bulk atmospheric deposition at two sites of the Seine estuary, one urban and one industrial, has been investigated. The PAH profiles indicate that PAHs mainly have a pyrolytic origin, both in urban and industrial areas. PAH sources vary during the year with an increase of high molecular weight PAH proportions (especially for carcinogenic PAHs) in winter, that means an increase of combustion processes such as domestic heating. Ratios of indicator PAHs (FTH/FTH+PYR and IcdP/IcdP+BghiP) confirm the pyrolytic origin of PAHs. In summer, ratios show the presence of industrial sources. In addition to these two methods, a factor analysis/multiple linear regression model was applied and gave an approximation of PAH source apportionment. PAH were found to be associated predominantly with emissions from road traffic (gasoline and diesel), that accounts for 17-34%. Domestic heating is a very important PAH source in urban areas and accounts for up to 85% of PAHs in winter. Industrial emissions (refineries...) account for 25% in the industrial area in summer. Each is an identified source category for the region and these results are consistent with fly-ashes identified by scanning electron microscopy. This study demonstrates that a combination of source identification methods is a far more efficient than one method alone.     

Enhanced ozonation of simulated dyestuff wastewater by microbubbles

The ozonation of synthetic wastewater containing azo dye, CI Reactive Black 5, was investigated using a microbubble generator and a conventional bubble contactor. The microbubble generator produced a milky and high intensity microbubble solution in which the bubbles had a mean diameter of less than 58 microm and a numerical density of more than 2.9 x 10(4) counts ml(-1) at a gas flow rate of less than 0.5 l min(-1). Compared with the bubble contactor, the total mass transfer coefficient was 1.8 times higher and the pseudo-first order rate constant was 3.2-3.6 times higher at the same initial dye concentration of 100 mg l(-1), 230 mg l(-1) and 530 mg l(-1) in the proposed microbubble system. The amount of total organic carbon removed per g of ozone consumed was about 1.3 times higher in the microbubble system than in the bubble contactor. The test using terephthalic acid as the chemical probe implied that more hydroxyl radicals were produced in the microbubble system, which contributed to the degradation of the dye molecules. The results suggested that in addition to the enhancement of mass transfer, microbubbles, which had higher inner pressure, could accelerate the formation of hydroxyl radicals and hence improve the oxidation of dye molecules.     

Influence of iron-bearing phyllosilicates on the dechlorination kinetics of 1,1,1-trichloroethane in Fe(II)/cement slurries

This study examines the effect of iron-bearing phyllosilicates on dechlorination rates of chlorinated aliphatic hydrocarbons (CAHs) in iron-based degradative solidification/stabilization (DS/S-Fe(II)). Laboratory batch experiments were conducted to evaluate dechlorination rates of 1,1,1-trichloroethane (1,1,1-TCA) in a mixture solution of Fe(II), cement and three different iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite). A first-order rate model was generally used to describe the dechlorination kinetics and the rate constants were dependent on soil mineral type (biotite, vermiculite, and montmorillonite), Fe(II) dose, and the mass ratio of cement to soil mineral. The pseudo-first-order rate constant for montmorillonite was lower than that for biotite and vermiculite by factors of 11-27 when the mass ratio of cement to phyllosilicates was fixed at one. The presence of biotite and vermiculite increase and the presence of montmorillonite decrease the degradation rate that would be observed in their absence. The effect of cement/mineral ratio on rate constants with three different soil minerals indicates that biotite was more reactive than the other two phyllosilicates. This may be due to high accessible natural Fe(II) content in biotite. Montmorillonite appears to inhibit dechlorination by either inactivating Fe(II) by ion exchange or by physically blocking active sites on cement hydration products.     

Measuring the flux at the interface of coal-tar impacted sediment and river water near a former MGP site

Determining water movement through contaminated sediment is critical for characterizing transport of chemicals from the sediment to the overlying water. Field studies to characterize the water flow across the sediment-water interface within a river adjacent to a former manufactured gas plant site were conducted. For this purpose, a new design of an interfacial flow meter was developed and tested. The in situ components of the system consisted of: a cylinder with an interfacial area of 2342 cm2; a dome attached to the cylinder; and a flow tube that allows water to flow from inside the dome to the river at the rate equal to the specific discharge across the sediment-water boundary. A 'heat-pulse' method was used to measure flow by heating the center of the flow tube for a brief time period and measuring the temperature profile within the tube over time. The system was calibrated to measure volumetric flux in the range 1.5-4.0 cm d(-1), however using a flow-addition method, the measurement of lower velocities also was accomplished, and calibration at higher fluxes is possible. From the groundwater flow at the interface of the coal-tar impacted sediment and information on the sediment pore water concentrations of several PAHs (poly-cyclic aromatic hydrocarbons), the mass flux of these PAHs to the river were estimated. Information on PAH mass flux at the sediment-water interface is useful for site assessment, including the evaluation of remediation alternatives and longer term site characterization.     

EDTA and urease effects on Hg accumulation by Lepidium sativum

The phytoextraction process was conducted under laboratory conditions with the use of garden cress plants (Lepidium sativum). The experiment was carried out in a model soil, which was characterized before conducting the process. Inorganic forms of mercury (HgCl(2), HgSO(4), Hg(NO(3))(2)) were used for contamination of the soil. The phytoextraction process was conducted after EDTA application to the soil and after urease application. Also the influence of simultaneous addition of ethylenediaminetetraacetic acid (EDTA) and urease into the soil on phytoextraction process was measured. In all variants of phytoextraction process the total mercury concentrations in roots, stems and leaves of garden cress were determined. The result showed that garden cress accumulated mercury from soil. The overall maximum concentration of mercury in its compounds was found in roots of the plant. In all cases, before addition of urease and EDTA, the translocation process and distribution of mercury in the plant tissues were limited. The addition of urease caused an increase of enzyme activity in the soil and at the same time caused an increase of mercury concentration in plant tissues. Application of EDTA increased solubility of mercury and caused an increase of metal accumulation by plants. After simultaneous addition of EDTA and urease into the soil garden cress accumulated about 20% of total mercury concentration in the soil. Most of mercury compounds were accumulated in leaves and stems of the plants (46.0-56.9% of total mercury concentration in the plant tissues).     

Effect of submergence-emergence sequence and organic matter or aluminosilicate amendment on metal uptake by woody wetland plant species from contaminated sediments

Site-specific hydrological conditions affect the availability of trace metals for vegetation. In a greenhouse experiment, the effect of submersion on the metal uptake by the wetland plant species Salix cinerea and Populus nigra grown on a contaminated dredged sediment-derived soil and on an uncontaminated soil was evaluated. An upland hydrological regime for the polluted sediment caused elevated Cd concentrations in leaves and cuttings for both species. Emergence and soil oxidation after initial submersion of a polluted sediment resulted in comparable foliar Cd and Zn concentrations for S. cinerea as for the constant upland treatment. The foliar Cd and Zn concentrations were clearly higher than for submerged soils after initial upland conditions. These results point at the importance of submergence-emergence sequence for plant metal availability. The addition of foliar-based organic matter or aluminosilicates to the polluted sediment-derived soil in upland conditions did not decrease Cd and Zn uptake by S. cinerea.     

The effects of fenvalerate on different tissues of freshwater fish Cirrhinus mrigala

The histopathological changes of fenvalerate on the gill, kidney, liver and intestine tissues of the Cirrhinus mrigala were determined by light microscopy. The fish were exposed to two sub-lethal concentrations of fenvalerate (1.5-3.0 ppb). The most common gill changes at all concentrations of fenvalerate were epithelial hyperplasia, epithelial necrosis, desquamation and lamellar fusion. Besides, epithelial lifting, oedema, swelling at the tips of secondary lamellae and curling of secondary lamellae were other histopathological changes. Necrosis of tubular epithelium, pycnotic nuclei in the hematopoietic tissue, hypertrophied epithelial cells of renal tubules, narrowing of the tubular lumen, expansion of space inside the Bowman's capsule and contraction of the glomerulus were observed in kidney tissues of fish. Hepatic lesions in the liver tissues of fish exposed to fenvalerate were characterized by congestion, cloudy swelling of hepatocytes and focal necrosis. Atrophy of epithelial cells, necrosis of epithelial cells, desquamation of mucosal epithelium and infiltration of lymphocytes into the lamina propria were detected in intestine tissues of fish after exposure to fenvalerate.     

Accumulation of polonium 210Po in tissues and organs of deer carvidae from Northern Poland

This study was undertaken to provide information on accumulation of polonium in tissues and organs of deer carvidae in order to assess the potential transport of this element via food-chain to game meat consumers. Livers, kidneys and muscles of large herbivorous animals belonging to three species: roe deer (Capreolus capreolus), red deer (Cervus elaphus) and fallow deer (Dama dama), collected in Northern Poland, were the subject of the present investigation. Activities of (210)Po were determined by means of alpha spectrometry along with relevant radiochemical procedures. The concentration of (210)Po in analyzed animals decreased in the order kidney > liver > muscle tissue. The average activity concentrations of (210)Po ranged between 0.02 +/- 0.01 Bq. kg(- 1) w.w. in muscles and 7.15 +/- 0.12 Bq. kg(- 1) w.w. in kidneys. Levels of polonium were not influenced by sampling location, sex, age and species of animals.     

Is an adjusted rhizosphere-based method valid for field assessment of metal phytoavailability? Application to non-contaminated soils

Previously recommended rhizosphere-based method (RHIZO) applied to moist rhizosphere soils was integrated with moist bulk soils, and termed adjusted-RHIZO method (A-RHIZO). The A-RHIZO and RHIZO methods were systematically compared with EDTA, DTPA, CaCl2 and the first step of the Community Bureau of Reference (BCR1) methods for assessing metal phytoavailability under field conditions. Results suggested that moist bulk soils are equally suited or even better than rhizosphere soils to estimate metal phytoavailability. The A-RHIZO method was preferred to other methods for predicting the phytoavailability of Ni, Cu, Zn, Cd, Pb and Mn to wheat roots with correlation coefficients of 0.730 (P<0.001), 0.854 (P<0.001), 0.887 (P<0.001), 0.739 (P<0.001), 0.725 (P<0.001) and 0.469 (P<0.05), respectively. When including soil properties, other extraction methods were also able to predict phytoavailability reasonably well for some metals. Soil pH, organic matter and Fe-Mn oxide contents, and cation-exchange capacity mostly influenced the extraction and phytoavailability of metals.