The use of respirometric measurements to determine the toxicity of textile dyes in aqueous solution and after oxidative decolourisation processes

Selected results from the degradation of reactive-dye hydrolysates after UV irradiation, ozonation and sodium peroxodisulphate (NaPS) treatment are presented. Reactive dyes with representative chromophores and anchor groups were chosen for the research project. Different stages of oxidative decolourisation were examined and determined by water parameters for biological degradation (BOD). The paper focuses on toxicity tests with Pseudomonas putida to consider whether the oxidative treatments result in products with a risk for the environment. Tests were performed with the AQUALYTIC^® Sensomat System, which measures biological oxygen demand (BOD). It was determined that the chosen oxidative treatments had as a rule no bearing on respiration of P. putida. Experiments with hydrolysates after short-term UV irradiation resulted in a slightly increased but not long-lasting toxicity in comparison with treatments with ozone or NaPS. Toxic effects were found in tests with hydrolysates of metalliferous dyes. During oxidative treatment, metals were liberated from the chromophores. This did cause complete inhibition of respiration of P. putida. Dye Blue E, a member of a dye class with chlorotriazine anchor groups, was itself found to be toxic, caused by the reactivity of the anchor group. The hydrolysate is only of minor toxicity.     

Cytotoxicity of TBBPA and effects on proliferation, cell cycle and MAPK pathways in mammalian cells

Poly-brominated flame retardants are ecotoxicologically relevant chemicals that can show high persistency in environmental samples and bioaccumulation in marine and fresh water animals. One of the most widely used compound is tetrabromobisphenol A (TBBPA). Until today, the toxicological data are rather fragmentary. Our studies on acute and sub-acute toxic effects with established cell lines demonstrate that TBBPA interferes with cellular signaling pathways. Cell viability is significantly reduced in a time- and concentration-dependent manner. The observed EC50 for rat kidney cells (NRK) was 52 microM (27 mg/l), 168 microM (90 mg/l) for A549 human lung cells, and 200 microM (108 mg/l) for Cal-62 human thyroid cells, respectively. The comparison of TBBPA with the non-brominated substance bisphenol A (BPA) clearly demonstrates that only the brominated compound exerts these effects on proliferation and cell viability. Cell cycle regulation was influenced considerably in Cal-62 cells, showing an explicit G2/M arrest in the cell cycle at TBBPA concentrations higher than 75 microM. Cellular signaling pathways directly connected to these affected parameters, e.g. the mitogen activated protein kinase (MAPK) cascades, are partly influenced in a cell specific and dose dependent manner. The extracellular-signal regulated kinase (ERK) is deactivated in NRK and A549 cells and activated in Cal-62 cells with increasing TBBPA concentrations.     

Ground laser remote sensing measurements of a Saharan dust outbreak in Central Spain. Influence on PM10 concentrations in the lower and upper Spanish plateaus

This paper presents the hourly evolution of a severe Saharan dust outbreak, (SDO), affecting Central Spain over July 23-24, 2004 measured with a laser remote sensing device at a location close to the Guadarrama mountain range foothills and its impact on PM10 levels (particles with an aerodynamic diameter below 10 microm) recorded at four contrasting monitoring stations located in the upper and lower Spanish plateau, some 170km apart. During the period of study the Saharan dust layer, (SDL), presented significant hourly variability in height (3600-1500m), depth (1500-700m) and aerosol dust loading (extinction coefficient, EC, 0.22-1.28km(-1)). Overnight layering was generally observed whereas a well mixed layer prevailed in the afternoon. The (SDO) impact on the lower levels took place approximately 12h after the (SDL) was initially observed and triggered by a descending dust enriched, evidencing the important role of subsidence over the presence of dust in lower altitudes. During the event, PM10 levels at all the stations exceeded EU air quality daily mean standards, 50 microgm(-3), on 2-4days. The maximum values ranged from 185 to 245 microgm(-3) depending on the monitoring station. The impact on PM10 spread from 2days in the upper plateau to 3-4 in the lower plateau, in agreement with the geographical location of the monitoring stations with respect to the southwest origin of the intrusion. The impact was even more dramatic on PM10 hourly concentrations, leading to maximum hourly peaks ranging from 322 to 598 microgm(-3) again depending on the monitoring station. Correlations between EC vertical profiles and PM10 hourly concentrations at the monitoring stations showed the great influence of the (SDO) on surface concentrations. The best linear fits corresponded to the extinction coefficients in the lower altitudes (close to the lower range of the device 500-650m), EC2, yielding satisfactory correlation coefficients ranging from 0.68 to 0.71. The low variability of the slope of each individual linear fit, 19.2%, shows the similar impact of (SDO) on the PM10 hourly concentrations recorded in the area under study.     

Nuclear magnetic resonance spectral characterization and semi-empirical calculations of conformations of alpha- and gamma-1,2,5,6,9,10-hexabromocyclododecane

The full 1H and 13C NMR spectral characterization of alpha- and gamma-1,2,5,6,9,10-hexabromocyclododecane (HBCD) is reported in this paper. The use of various NMR experiments, an analysis of the magnitude of the NMR chemical shifts and coupling constants, and computer modeling has enabled the visualization of the three-dimensional structures for both the alpha- and gamma-diastereomers. This information may provide insight into the different behavior of the alpha- and gamma-HBCD diastereomers in the environment.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Investigation of the removal of heavy metals from sediments using rhamnolipid in a continuous flow configuration

Heavy metal contamination of sediments is hazardous to benthic organisms and needs more attention in order to prevent entry of these heavy metals into the food chain. Biosurfactants have shown the capability to remove heavy metals from soils and sediments. The objective of this research was to evaluate the performance of rhamnolipid, a glycolipid biosurfactant, in a continuous flow configuration (CFC) for removal of heavy metals (copper, zinc, and nickel) from the sediments taken from Lachine Canal, Canada, to simulate a flow through remediation technique. In this configuration, rhamnolipid solution with a constant rate was passed through the sediment sample within a column. Important parameters such as the concentration of rhamnolipid and the additives, time and the flow rate were investigated. The removal of heavy metals from sediments was up to 37% of Cu, 13% of Zn, and 27% of Ni when rhamnolipid without additives was applied. Adding 1% NaOH to 0.5% rhamnolipid improved the removal of copper by up to 4 times compared with 0.5% rhamnolipid alone. This information is valuable for designing a remediation protocol for sediment washing.     

Sources of adsorbable organic halogens (AOX) in sludge of Gaza

Average concentrations of adsorbable organic halogens (AOX) in sludge from the Gaza Strip reached 600 mg kg(-1) which currently represents a major limiting factor for sludge application in agriculture. This study aims to identify the main sources of AOX in Gaza where the area is small with limited industrial activities. The results showed that the AOX in effluent sludge is formed mainly inside the treatment plant. Although the plant receives AOX wastewater of only 85 microg l(-1), this value increased five fold inside the plant to an average of 400 microg l(-1) in the effluent wastewater. On the other hand, the sludge from the first sedimentation pond showed an AOX concentration of 213 mg kg(-1) and increased in the final sedimentation pond to 500 mg kg(-1). The AOX concentration in three month old sludge was 130 mg kg(-1). The textile and detergent industries are the major AOX producing industries in Gaza, with an average AOX of 40,000 microg l(-1) in their effluent wastewater. These values do not represent a significant AOX pollution load to the treatment plant because these industries are very limited and their effluents are diluted before entering the municipal treatment plant. Industrial activity decreased in 2006 to less than 70% of the previous four years. Consequently, the AOX in the industrial effluent decreased from 150,000 to 40,000 microg l(-1) over the same time period. Sludge from these industries showed 1300 mg kg(-1) AOX for the past four years and only 400 mg kg(-1) in 2006. Moreover, the AOX in the influent wastewater discharged to the treatment plant decreased from 320 to 85 microg l(-1) for the same period. This study revealed that the major AOX is formed inside the treatment plant and especially in the anaerobic facilities. There was no correlation between the AOX concentrations in the sludge and the wastewater at the same location. Moreover, there was no correlation between the AOX in sludge/wastewater and dissolved oxygen, pH and chloride in that treatment plant.     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.     

Investigating interactions of phenanthrene with dissolved organic matter: limitations of Stern-Volmer plot

Although linear binding isotherms of hydrophobic organic chemicals (HOCs) with dissolved organic matter (DOM) are widely reported, several studies showed nonlinear HOC-DOM interactions. This study pointed out that fluorescence static quenching modeling (FSQM), which often uses a Stern-Volmer type plot to process the data from fluorescence quenching experiments, is conceptually different from the classic Stern-Volmer equation. We also emphasized that although linear Stern-Volmer plots are generally observed in literature, it does not necessarily indicate a linear HOC-DOM interaction. According to both mathematical simulation and laboratory sorption experiments in this study, nonlinear interactions could be concealed by the use of Stern-Volmer plot. Moreover, this study tested the two assumptions for applying FSQM to process binding data. Our results showed that binding coefficient (K(DOC)) for phenanthrene is neither independent of free solute concentration, nor DOM concentration, which is a critical limitation for using FSQM in a form of Stern-Volmer equation to examine HOC-DOM interactions. Therefore, the true characteristics of HOC-DOM interactions need to be examined using different ways of experimental design and data processing.     

The weaker points of fish acute toxicity tests and how tests on embryos can solve some issues

Fish acute toxicity tests play an important role in environmental risk assessment and hazard classification because they allow for first estimates of the relative toxicity of various chemicals in various species. However, such tests need to be carefully interpreted. Here we shortly summarize the main issues which are linked to the genetics and the condition of the test animals, the standardized test situations, the uncertainty about whether a given test species can be seen as representative to a given fish fauna, the often missing knowledge about possible interaction effects, especially with micropathogens, and statistical problems like small sample sizes and, in some cases, pseudoreplication. We suggest that multi-factorial embryo tests on ecologically relevant species solve many of these issues, and we shortly explain how such tests could be done to avoid the weaker points of fish acute toxicity tests.