Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.     

Interpretation of heavy metal data from mussel by use of multivariate classification techniques

Different strategies of multivariate analysis of metals concentrations (Mn, Fe, Ni, V, Co, Cu, Cd, Hg, Pb, Na, K) in mussel samples from different spanish markets are used to interpret a data base and identify differences between species and origin of the samples. Principal Component Analysis and Potential curves are applied to properly classify unknown samples from representative mussels samples (Mytilus edulis and Perna canaliculus). Also, Principal Components Analysis is used as display method to visualize the relation between the variables and objects of interest.     

Tissue distribution of planar and non-planar chlorobiphenyls, 4,4'-DDE and hexachlorobenzene in sheep and lambs

The bioconcentration and distribution pattern of individual PCB congeners (IUPAC Nos: -54, -80, -155 and -169) and organochlorine pesticides (HCB and 4,4'-DDE) in blood, adipose tissue, liver and brain were examined in sheep two months after administration and in their offspring continuously exposed during the two months lactation period. Analyses were performed by high resolution gas chromatography. The levels of individual organochlorines varied significantly between tissues; the tissue/blood ratio (on a fat basis) varied by two orders of magnitude for individual congeners. The bioconcentration of the toxic planar PCB-169 congener was the highest in the liver and the lowest in the brain of the sheep.     

Clearance of PCDD/Fs via the gastrointestinal tract in occupationally exposed persons.

A digestive tract mass balance was performed on six men with high body burdens of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Intake via food was measured by analyzing duplicate portions of the food consumed by the volunteers and excretion via feces was determined by quantitative collection and analysis of the feces. Blood samples were taken to determine the current body burden. The results showed that the quantity of non-metabolized chemical excreted in the feces clearly exceeded the uptake via food for all of the 2,3,7,8-substituted PCDDs and some of the PCDFs, indicating a significant clearance across the gastrointestinal tract. The concentrations of these PCDD/F congeners in blood and feces were highly correlated (r > 0.8), demonstrating that the fecal PCDD/F content was determined by the body burden. The half lives in the test persons due to fecal clearance of non-metabolized chemical were estimated from the excretion rate and the current body burden and ranged between 10 years (Cl8DD) and 33 years (2,3,4,7,8-Cl5DF). These were compared with the overall contaminant half-lives due to all clearance processes which were calculated from the body burden and the decrease in blood concentrations measured over several years. The fecal clearance of non-metabolized PCDD/F contributed on average between 37% (2,3,7,8-Cl4DD) and 90% (Cl8DD) to the total elimination. This indicates that the gastrointestinal pathway plays a decisive role in the clearance of most 2,3,7,8-subsituted PCDD/F congeners.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Vanadium contamination and the relation between vanadium and other elements in wild birds

There is little information on vanadium (V) contamination in wildlife. In the present study, the mean V contents in liver and kidney from 41 wild Japanese water birds were less than 3.69 and 8.11 microg/g dry wt, respectively. The V contents in the liver and kidney of the spotbill duck were more than two times higher than those of other species in Japan. Spotbill ducks obtained in a residential district had a strong correlation between the V contents in the kidneys and those in the livers (R=0.924), and also between V and Ti, Cd, and Li contents in the liver (R>0.8). These results suggest that V accumulation in wild birds reflects the degree of environmental contamination.     

Measurements of peroxyacyl nitrates (PANS) in Mexico City: implications for megacity air quality impacts on regional scales

Peroxyacyl nitrates (PANs) were measured using gas chromatography with electron capture detection (GC/ECD) in north central Mexico City during February–March of 1997. Peroxyacetyl nitrate (PAN) was observed to exceed 30 ppb during five days of the study, with peroxypropionyl nitrate (PPN) and peroxybutryl nitrate (PBN) reaching 6 and 1 ppb maximum, respectively. Levels of total PANs typically exceeded 10 ppb during the period of measurement and showed a very strong diurnal variation with PANs maximum during the early afternoon and falling to less than 0.1 ppb during the evening hours. These levels of PANs are the highest reported values in North America (and the world) for an urban center, since levels of approximately 30 ppb were reported during the late 1970s in the Los Angeles area (South Coast Air Basin, Tuazon et al., 1978). Hydrocarbon measurements indicate that the levels of olefins, specifically butenes are significant in Mexico City. A time series taken of source indicator hydrocarbons taken before and during a Mexican National Holiday with reduced automobile traffic clearly show that mobile sources of butenes are as important as liquefied petroleum gas. Observations of 10–40 ppb C methyl-t-butyl ether (MTBE) are consistent with MTBE/gasoline fuel usage as a source of isobutene and formaldehyde. Both these reactive species can lead to increased oxidant and PAN formation. The strong diurnal profiles of PANs are consistent with regional clearing of the Mexico City air basin on a daily basis. Estimates are given using a simple box model calculation for a number of key primary and secondary pollutant emissions from this megacity on an annual basis. These calculations indicate that megacities can be important sources of both primary and secondary pollutants, and that PANs produced in megacity environments are likely to contribute strongly to regional scale ozone and aerosol productions during long range transport.     

Ozone patterns for three metropolitan statistical areas in North Carolina, USA

As part of an effort by the state of North Carolina to develop a State Implementation Plan (SIP) for 1-h peak ozone control, a network of ozone stations was established to monitor surface ozone concentrations across the state. Between 19 and 23 ozone stations made continuous surface measurements between 1993 and 1995 surrounding three major metropolitan statistical areas (MSAs): Raleigh/Durham (RDU), Charlotte/Mecklenburg (CLT), and Greensboro/High Point/Winston-Salem (GSO). Statistical averages of the meteorological and ozone data were performed at each Metropolitan Statistical Area (MSA) to study trends and/or relationships on high ozone days (days in which one of the MSA sites measured an hourly ozone concentration90.0 ppbv). County emission maps of precursor gases, wind roses, total area averages of ozone, total downwind averages of ozone deviations, upwind averages of ozone, and a modified delta ozone analysis were all obtained and analyzed. The results of this study show a reduction in the delta ozone relative to an earlier study at RDU, but no average significant change at CLT (no comparison can be made for GSO). The statistical data analyses in this study are used to quantify the importance of local contributions and regional transport, to ozone air pollution in the MSAs.     

Organochlorine pesticide residues in human milk in Punjab, India

Human milk samples collected from areas having intensive cotton cultivation and sparse cotton cultivation in Punjab (India) were analysed for organochlorine insecticides. Both DDT and HCH were detected in almost all the samples analysed. The average levels of Sigma-DDT and Sigma-HCH residues in samples from cotton-growing areas were significantly higher than in those from areas where cotton is sparsely grown. Residues of Sigma-DDT mainly comprised p,p'-DDT and p,p'-DDE, while those of Sigma-HCH residues were mainly in the form of its beta-isomer. Median values of 0.52 microg g(-1) of Sigma-DDT and 0.19 microg g(-1) of Sigma-HCH in samples of human milk from cotton-growing areas of Punjab (India) were higher than those reported from most other countries in the World.     

Retrieval of heavy metal ions from solution via ferritisation

The paper summarises the results of the studies on retrieval of heavy metal ions in solution by ferritisation and its potential application in waste-water treatment. The optimum procedure for ferritisation of heavy metal ions in solution has been evolved with respect to pH, concentration of Fe2+, rate and time of aeration and temperature. The recommended procedure consists of controlled aeration of the solution containing heavy metal ions and ferrous ions at pH 9.5-10.5 at about 50 degrees C, until the black, granular, magnetic ferrite separates out. The metal ferrites can also be formed, even without heating or forced aeration, by ageing the mixed metal hydroxide precipitate at pH 10 to 11. The metal ferrites formed have been characterised by X-ray diffractometry. The laboratory-scope experiments conducted with synthetic heavy metal solutions as well as actual wastewater from a tanning industry showed that heavy metal ions can be effectively removed from solution to sub-ppm levels. The metal ferrites thus recovered may find commercial application as microwave absorbers, catalysts, metal scavengers, etc. This technique seems to have potential application in simultaneous, one step removal of different heavy metal ions from industrial wastewaters.