Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater

The photodegradation and biodegradability have been investigated for four non-biodegradable commercial azo dyes, Reactive YellowKD-3G, Reactive Red 15, Reactive Red 24, Cationic Blue X-GRL, an indicator. Methyl Orange, and one industrial wool textile wastewater, using TiO2 suspensions irradiated with a medium pressure mercury lamp. The color removal of dyes solution and dyeing wastewater reached to above 90% within 20-30 min. of photocatalytic treatment. Biochemical oxygen demand (BOD) was found to increase, while chemical oxygen demand (COD), total organic carbon (TOC) decreased, so that the ratio of BOD5/COD of the wastewater increased from original zero up to 0.75. The result implies that photocatalytic oxidation enhanced the biodegradability of the dye-containing wastewater and therefore relationship between decolorization and biodegradability exists. When the color disappeared completely, the wastewater biodegraded normally and could be discharged for further treatment. The experimental results demonstrate that it is possible to combine photocatalysis with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable azo dyes.     

Distribution in Portugal of some pollutants in the lichen Parmelia sulcata

During the months of July and August 1993 a lichen (Parmelia sulcata Taylor) collection campaign was held in Portugal where samples were obtained from olive tree bark at 228 sites, following a grid of 10 x 10 km along the Atlantic coast and 50 x 50 km in the interior of the country. The samples were analysed by instrumental neutron activation analysis and proton induced X-ray emission techniques. Concentration data patterns for the pollutants As, Cr, Hg, Ni, Pb, S, Sb, Se, and V were obtained for the whole country surface by making use of an extinction rule of 1/r(3), preventing any cut-off distance from being artificially introduced. Some pollution sources were identified: (1) oil-powered plants on the Lisbon-Setúbal axis (V, Ni), (2) coal-power plants in Porto and Sines (S, Se), (3) traffic in the northern area and the Lisbon-Setúbal axis (Pb), (4) a chemical industry south of Porto (Hg, As), and (5) soil influence (Cr, Sb). Arsenic and chromium results largely exceed, in a few areas, the concentrations acceptable to plants, and in a few spots also Hg, Ni, and Pb data.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

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.     

Short-term effects of metals on the filtration rate of the zebra mussel Dreissena polymorpha

In order to study the short-term ecotoxicity of metals to the freshwater mussel Dreissena polymorpha, the effects of Cu, Zn and Cd on the filtration rate of this mussel were determined in laboratory experiments. Filtration rate was chosen as the endpoint, because it is a sensitive sublethal parameter compared to mortality and it is an important parameter given the ecological role D. polymorpha fulfills. The filtration rate was calculated from the decrease in algal concentration, fed to mussels in aquaria, containing different metal concentrations. The EC50 for Cu (41 microg litre(-1)) was lower than for Cd (388 microg litre(-1)) and Zn (1350 microg litre(-1)). The NOEC(accumulation) for the essential metal Zn was higher than for the essential metal Cu. Cadmium, a non-essential metal, was accumulated at all elevated water concentrations, so the NOEC(accumulation) was the concentration in the control water (<0.2 microg litre(-1)). All (no) effect concentrations found in this study were above the quality criteria set for metal concentrations in Dutch surface water, suggesting that the zebra mussel is sufficiently protected by these quality criteria.     

Polycyclic aromatic compounds in Northwest Atlantic COD (Gadus morhua)

Twenty-seven polycyclic aromatic compounds (PAC) including polycyclic aromatic hydrocarbons (PAH) and polycyclic aromatic sulphur heterocycles were analysed in muscle, liver and ovaries of cod (Gadus morhua) from the Northwest Atlantic. These PAC include the 16 PAH priority pollutants (EPA recommendation), alkylated naphthalenes, phenanthrene-anthracenes as well as dibenzothiophenes (DBT). Aromatics were undetectable in muscle. One of the analysed PAC was detected in one ovary and six in another ovary sample. Liver samples contained between 1 and 9 PAC. Of the parental PAH, only acenapthene (18 ng/g, dry weight), fluorene (28 ng/g) and chrysene (22 ng/g) were detected once each in two liver samples, while fluorene (72 ng/g) was detected once in one of the ovaries. C-2 DBT was the major component in ovaries and liver (8-86 ng/g), while C-3 and C-4 alkylated phenanthrene-anthracene (12-78 ng/g) were the next major components detected in the liver samples. This is the first detailed study of PAH and PAC in finfish from the Northwest Atlantic.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 2-Polychlorinated biphenyls

The temporal variability and bioaccumulation dynamics of individual PCBs were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the polluted Buenos Aires coastal area. Fish muscles contain high concentrations of total PCBs (11+/-7.2, 4.6+/-3.4 or 19+/-13 microg g(-1), dry, fresh and lipid weight, respectively) reflecting chronic bioaccumulation from sewage-industrial particulates. On a temporal basis, lipid normalized PCBs concentrations peaked by the end of 2001-2002 coincident with the rainiest period over the last four decades and shortly after PCB prohibition in the country, reflecting massive discharges to the coastal ecosystem. PCB composition in fish muscles show a prevailing contribution of hexachlorobiphenyls (35+/-4.2%), followed by hepta (23+/-3.0%), penta (20+/-3.6%), tri-tetra (16+/-4.8%) and minor proportions of octa-decachlorobiphenyls (5.7+/-3.1%) similar to an Aroclor 1242-1254-1260 1:2:4 mixture. During 2001-2002 maxima fish showed an enrichment in tri-tetrachlorobiphenyls ( approximately 1242-1254-1260 1:1:1 mixture) denoting a fresher signature. Fish/settling material lipid-organic carbon accumulation factors (BSAFs: 2.4-46, average: 21+/-10) plotted against kow showed a parabolic trend (BSAFs=-0.38 log kow2 + 5.16 log kow -15.85; R2=0.46) maximizing at hexa, hepta and octachlorobiphenyl 203 with reduced bioaccumulation of a few hepta (170, 191) and most octa-decachlorobihenyls suggesting limited intestinal absorption.     

Comparing computing formulas for estimating concentration ratios

The purpose of this paper is to provide guidance on the choice of computing formulas (estimators) for estimating average concentration ratios and other ratio-type measures of radionuclides and other environmental contaminant transfers between ecosystem components. Mathematical expressions for the expected value of three commonly used estimators (arithmetic mean of ratios, geometric mean of ratios, and the ratio of means) are obtained when the multivariate lognormal distribution is assumed. These expressions are used to explain why these estimators will not in general give the same estimate of the average concentration ratio. They illustrate that the magnitude of the discrepancies depends on the magnitude of measurement biases, and on the variance and correlations associated with spatial heterogeneity and measurement errors. This paper also reports on a computer simulation study that compares the accuracy of eight computing formulas for estimating a ratio relationship that is constant over time and/or space. Statistical models appropriate for both controlled spiking experiments and observational field studies for either normal or lognormal distributions are considered. Our results indicate that for either type of study the geometric mean is generally preferred if the lognormal distribution applies. However, the geometric mean has the disadvantage that its expected value depends on n, the number of measurements taken. Ricker's estimator, $\text{R}\text{?}{}_{\mathrm{rt}}$, appears to perform worse than the other estimators studied when the observations are lognormal. All eight estimators appear to be equally accurate for the controlled spiking study when data are normally distributed. For observational field studies when data are normally distributed the ratio of means or slight modifications thereof are preferred to other estimators investigated. Before one chooses a computing formula for estimating a concentration ratio, thought should be given to what target value needs to be estimated to satisfy study objectives, and to whether the normal or lognormal distribution is a more realistic model. The geometric mean performs well for lognormal distributions, but comparison of geometric means or of a geometric mean with environmental limits can be misleading if n is small. The arithmetic mean of ratios is a conservative choice in that it will always give a larger estimate than will the geometric mean. It may also be severely biased when data are lognormal and the variances of measurement errors are large. The ratio of the means is a reasonable choice if the distribution is normal. The median of the observed ratios, $\text{R}\text{?}{}_{\mathrm{<mtext>md</mtext>}}$, is useful estimate since it is easily obtained and has an easily understood interpretation as the point above which and below which 50% of the observed ratios lie. Also, it is appropriate no matter what the distribution of the observed ratios may be. Confidence limits on the median are also easily obtained. Finally, while this paper emphasizes applications in radionuclide research, our results should be applicable to a wide range of environmental contaminants since many contaminants have approximately lognormal distributions.