Inorganic greywater matrix impact on photocatalytic oxidation: does flocculation of TiO2 nanoparticles impair process efficiency?

This study was conducted in order to clarify whether photocatalyst flocculation--as observed in biologically pretreated greywater--contributes to photocatalytic oxidation (PCO) efficiency impairment. Aqueous solutions of tetraethyleneglycol dimethylether spiked with different inorganic salts in concentrations as found in biologically treated greywater were investigated with respect to TiO2 flocculation and PCO mineralisation kinetics. Flocculation of the photocatalyst primarily depended on pH (which was affected by the salts) and how close pH was to the point of zero charge (PZC). Photocatalyst agglomeration was maximum at pH 5.5. With salt concentrations >7 mmol L(-1), flocculation was strong even at pH far above PZC due to electric double layer compression. PCO rate constants were not unequivocally related to flocculation. Increasing pH was observed as the clearest factor deteriorating PCO efficiency. This was interpreted to result from impaired adsorbability of negatively charged oxidation intermediates as well as from enhanced CO2 absorption with increasing pH and subsequent formation of HCO3(-) anions which are OH radical scavengers.

Solar photocatalytic oxidation of pretreated wastewaters: laboratory scale generation of design data for technical-scale double-skin sheet reactors.

Batchwise heterogeneous photocatalytic oxidation of model wastewater (solutions of the azo dye "Acid Orange 7" in tap water) has been performed in a laboratory-scale stirred vessel reactor with non-submerged UV-A lamps using titanium dioxide "P25" as photocatalyst. Comparison to results of solar pilot-scale Plexiglass double-skin sheet reactor (DSSR) experiments indicates that the lab-scale method may predict area demand for technical-scale DSSR design. Characteristic UV-A fluences leading to TOC or COD reduction to e(-1) of the initial concentrations were determined in lab-scale stirred vessel experiments for treated effluents of seven different industrial branches, secondary municipal effluent and biologically treated greywater. Predicted areas for solar photocatalytic oxidation of these effluents in DSSRs yielding mineralization of 95% of organics in 100 m3 of the respective effluents for a TiO2 concentration of 2 g l(-1) and a sky and solar radiation of 3.9kWh m(-2) d(-1) within one day greatly varied from below 6,000 m2 (biologically treated lubricating oil refinery effluent) to more than 100,000 m2 (highly saline biologically treated effluent of chemical industry). Especially municipal and refinery effluents (except oil reclaiming) have been identified as promising candidates for reuse after solar photocatalytic oxidation. Mineralization efficiency was decreasing with increasing alkalinity of effluents. This was interpreted by competition of hydrogen carbonate anions with organics for binding sites on photocatalyst surface and by OH radical scavenging by hydrogen carbonate. Dependence on alkalinity was superimposed by salinity influence as some effluents with high alkalinity also exhibited high salt concentrations (especially chloride).

Freeze concentration for enrichment of nutrients in yellow water from no-mix toilets.

Separately collected urine ("yellow water") can be utilized as fertilizer. In order to decrease storage volumes and energy consumption for yellow water transport to fields, enrichment of nutrients in yellow water has to be considered. Laboratory-scale batch freeze concentration of yellow water has been tested in ice-front freezing apparatus: a stirred vessel and a falling film freeze concentrator (coolant temperatures: -6 to -16 degrees C). With progressing enrichment of the liquid concentrate, the frozen ice was increasingly contaminated with yellow water constituents (ammonia, total nitrogen, total phosphorus, TOC, and salts determined as conductivity). The higher the initial salinity of the yellow water and the lower the mechanical agitation of the liquid phase contacting the growing ice front, the more the frozen ice was contaminated. The results indicate, that in ice-front freezing devices multistage processes are necessary, i.e. the melted ice phase has to be purified (and the concentrates must be further enriched) in a second or even in a third stage. Energy consumption of this process is very high. However, technical scale suspension freeze concentration is reasonable in centralized ecological sanitation schemes if the population exceeds 0.5 million and distance of yellow water transportation to fields is more than 80 km.

Screening of chemical oxidation processes and other methods for decolorization of urine for its re-use as toilet-flush liquid in ecological sanitation systems.

Because of its potential use as fertilizer, urine ("yellow water") is a resource originating from sanitation. Its separate collection in no-mix toilets is a beneficial aspect of ecological (source control) sanitation. In order to avoid dilution of the fertilizing nutrients with toilet flush water, the utilization of yellow water as toilet flush liquid seems to be advantageous. To be accepted for this purpose, urine has to be decolorized (and also deodorized). In this study activated carbon adsorption, irradiation with UV light of different wavelengths, the advanced oxidation processes ultrasound, UV/H2O2, and photocatalytic oxidation have failed to decolorize urine. Biological treatment caused brown colour of the treated urine. Only ozonation was successful in colour removal, although it did not affect TOC. In spite of darkening of yellow water during biological treatment (generation of humic substances), smaller ozone doses were required for decolorizing the biologically pre-treated urine than for original urine. Photocatalytic oxidation of biologically treated urine also removed brown colour, but the original yellow colour remained. In ozonated urine, yellow colour was reconstituted unless hydrogen peroxide was added. In addition to colour removal, ozone contributed to deodorization as a consequence of ammonia stripping and probably of phenol oxidation.

Greywater treatment by constructed wetlands in combination with TiO2-based photocatalytic oxidation for suburban and rural areas without sewer system.

In this study greywater treatment through constructed wetlands and subsequently through TiO2-based photocatalytic oxidation was investigated. Through constructed wetlands treatment the organic substances have been reduced greatly. For further removal of organic substances and pathogens, a TiO2-based photocatalytic oxidation process was used subsequently. The results showed that the treated greywater through constructed wetlands and subsequent through TiO2-based photocatalytic oxidation with short irradiation time (3 hours irradiation time) met the requirements of European bathing water quality easily. Therefore, the greywater treated with the processes combination can directly be reused for non-potable purposes. Moreover, since residual organic substances through TiO2-based photocatalytic oxidation with long irradiation time can be eliminated almost totally, it is also possible that treated greywater is used for groundwater recharge as a drinking water resource.

Production of value added products from separately collected urine.

For many reasons it is advantageous to collect urine separately and collection systems, so called "no-mix-toilets" exist. Therefore, this work deals with some methods to make use of this urine to produce value added products: IBDU and ammonia water. It could be shown that urea can be converted to IBDU only after concentrating urine. With air stripping and absorption ammonificated urine can be treated very effectively and a solution of 10% w/w of ammonia can be obtained.

Cytotoxicity of dust constituents towards alveolar macrophages: interactions of heavy metal compounds.

The interactions between different heavy metal compounds which affect their cytotoxicity towards rabbit alveolar macrophages were investigated. The cells were exposed in vitro to combinations of As3+, Cd2+, Hg2+, Ni2+, or V5+ with different concentrations of another heavy metal compound. Toxicity was determined as the depression of zymosan-induced release of superoxide anion radicals. Significant antagonisms occurred in the combinations Cd2+/Zn2+, Hg2+/As3+, and Hg2+/Se4+, while significant synergisms were exhibited by the combinations Cd2+/Cu2+, Cd2+/Sn2+, Hg2+/Cu2+, Ni2+/Cd2+, Ni2+/Cu2+, Ni2+/Sn2+ and V5+/Cu2+. In the combinations As3+/Zn2+, Hg2+/Cd2+ and Hg2+/Zn2+, both kinds of interactions were observed depending on the concentrations of the heavy metal compounds. An interpretation of the measured heavy metal interactions with reference to the toxicity of heavy metal-containing dusts is attempted.

Zymosan-induced chemiluminescence of alveolar macrophages: depression by inorganic dust constituents.

A method has been developed which allows the incubation of alveolar macrophages as weakly affixed monolayers in siliconized glass dishes. Without vigorous mechanical agitation and without using proteolytic enzymes, these cells were subsequently transferred to cuvettes where the zymosan-stimulated chemiluminescence of the suspended cells was measured. In vitro incubations of activated rabbit alveolar macrophage monolayers with airborne dusts from four West German sites (1 to 200 micrograms/10(6) cells), fly ash fractions of a special waste incinerator at Hamburg (50 to 1,000 micrograms/10(6) cells), and quartz dust DQ 12 (5 to 200 micrograms/10(6) cells) resulted in a dose- dependent depression of the zymosan-stimulated chemiluminescence. The depression of chemiluminescence was correlated with particle numbers, estimated dust surface, and antimony and lead masses of the dusts to which the cells were exposed. Cytotoxicity was better correlated with these parameters than with dust mass.

Tetrachloroethene air pollution originating from coin-operated dry cleaning establishments.

In 15 coin-operated dry cleaning establishments (CODC), in one building where a CODC had been run and in a private car transporting a dry-cleaned down jacket tetrachloroethene (TCE) indoor concentrations were investigated by air sampling with activated carbon tubes, elution of the carbon with toluene, and subsequent gas chromatographic analysis of the eluate. TCE concentrations in the car transporting the garment were up to 24.8 mg/m3. Within CODC air concentrations between 3.1 and 331 mg/m3 were measured. In the building where a CODC had once been run the TCE concentrations were slowly decreasing after removal of dry cleaning machines. In the basement below the CODC the TCE air concentration was 155 mg/m3 immediately after removal of the machines and 4.5 mg/m3 7.5 months later. TCE migrated from the basement via the staircase to the flats of the second floor where TCE air concentrations were about 1% of the concentrations in the basement. TCE-contaminated building material is shown to be a reservoir causing increased TCE air concentrations for a long time, which is serious considering the carcinogenic and reproductive risks from TCE exposure.

Depression of alveolar macrophage hydrogen peroxide and superoxide anion release by mineral dusts: correlation with antimony, lead, and arsenic contents.

Activated rabbit alveolar macrophages were incubated with airborne dusts from four West German sites (1 to 200 micrograms/10(6) cells) and waste incinerator fly ash fractions (50 to 500 micrograms/10(6) cells). Quartz dust DQ 12 (5 to 200 micrograms/10(6) cells) and Fe2O3 (0.05 to 50 micrograms/10(6) cells) were used as control dusts. The zymosan-stimulated hydrogen peroxide and superoxide anion release of the macrophages were not affected significantly by Fe2O3. All other investigated dusts decreased the two cell functions which were correlated negatively with surfaces, particle numbers, and antimony, lead, and arsenic contents of the dusts. The influence of heavy metal antagonisms and dust surfaces on dust toxicity against alveolar macrophages is discussed.

Toxicity of metallic ions and oxides to rabbit alveolar macrophages.

The effects of soluble compounds and oxides of As, Cd, Cu, Hg, Ni, Pb, Sb, Sn, V, and Zn on oxidative metabolism and membrane integrity of rabbit alveolar macrophages were studied by 24-hr in vitro exposure. Oxidative metabolism induced by phagocytosis of opsonized zymosan was measured by H2O2 and O2- release and by chemiluminescence in the presence of luminol. Membrane integrity was estimated by extracellular LDH activity. Metallic ions and oxides inhibited the release of active oxygen species. Cd(II), As(III), and V(V) were the most toxic elements as measured by all investigated parameters. Cu(II) decreased O2- release and chemiluminescence effectively but H2O2 release and membrane integrity less. Chemiluminescence was decreased strongly by Hg(II) while O2- and H2O2 release were depressed moderately. Zn(II) and Sb(III) compounds caused medium toxicity and the tested Sn, Ni, and Pb compounds showed only faint toxic effects.

Cytotoxicity to alveolar macrophages of airborne particles and waste incinerator fly-ash fractions.

A waste incinerator fly ash was separated into different grain-size fractions by sieving and sedimentation in butanol. The element content of each fraction was determined by atomic absorption and emission spectrometry. The fly-ash fractions, an eluted fine fly-ash fraction and an eluted airborne dust were analysed microscopically for particle size and numbers, together with standard quartz DQ 12 and three element-analysed airborne dusts. Rabbit alveolar macrophages, isolated by lung lavage, were incubated for 24 h with the particulates, the two eluates and a mixed element compound solution corresponding to the element concentrations of one airborne dust. At the end of incubation, the activities of lactate dehydrogenase, N-acetyl-beta-glucosaminidase, beta-galactosidase and acid phosphatase were determined in medium and cell lysates. Cytotoxicity was expressed as ratio of extracellular to total LDH (lactate dehydrogenase) activity. Release of N-acetyl-beta-glucosaminidase and beta-galactosidase was correlated positively with LDH release, whereas the total activity of acid phosphatase decreased with increasing LDH release. Cytotoxicity of the dusts was correlated with particle numbers, and As, Sb and Pb contents. The contribution of As to particle toxicity is discussed. Eluates of dusts did not affect rabbit alveolar macrophage viability.

Effects of quartz, airborne particulates and fly ash fractions from a waste incinerator on elastase release by activated and nonactivated rabbit alveolar macrophages.

Elastase release from cultured, activated and nonactivated rabbit alveolar macrophages (AM) was investigated after stimulation by different environmentally related mineral dusts (50-1000 micrograms/10(6) cells). Eight different dusts were analyzed for element contents and grain size: one rural and three urban airborne dusts, a coarse and a fine fraction of a sieved waste incinerator fly ash, a sonicated coarse fly ash fraction, and the standard quartz dust DQ 12. The fine fly ash fraction, the sonicated coarse fly ash fraction, and the quartz dust DQ 12 enhanced elastase release by activated AM. Only one of the tested airborne dusts effected a comparable elastase release. The untreated coarse fraction of the fly ash did not cause a significant increase of extracellular elastase activities. Elastase release was dependent on particle numbers and chemical composition and correlated best with barium and tin contents. Nonactivated AM released higher elastase activities than activated AM at low-dose levels. The possible role of dust-induced elastase secretion in the pathogenesis of emphysema is discussed.