Solvent and surfactant enhanced solubilization, stabilization, and degradation of amitraz

In an effort to help with the development of effective dip vat management and waste disposal strategies this study determined how solution properties such as pH, buffer composition, ionic strength, temperature, solubility in organic solvents and the addition of commonly used solubilizing agents influenced the hydrolysis of amitraz. Amitraz degrade by means of hydrolysis described by a pseudo-first order rate process and a type ABCD pH rate profile. Hydrolysis increased with temperature and was fastest at low pH, slowest at neutral to slightly alkaline pH, and slightly increased above pH 10. However, buffer concentration and ionic strength influenced the hydrolysis rate and had to be accounted for before constructing a pH rate profile. Hydrolysis seems to depend on the dielectric constant of solvent mixtures and was fastest in water, slower in propylene glycol and ethanol solutions, and slowest in DMSO mixtures. In surfactant solutions, anionic micelles enhanced and cationic micelles retarded the hydrolysis rate. The magnitude of micellar effects decreased with increasing concentrations of the surfactants. The increased solubility and faster hydrolysis of amitraz in the sodium lauryl sulfate solutions showed that anionic surfactants potentially could be used for cleaning up amitraz spills, because it both solubilized the drug and catalyzed hydrolysis.     

Degradation of toxaphene in water during anaerobic and aerobic conditions

The degradation of technical toxaphene in water with two kinds of bioreactors operating in sequence was studied. One packed bed reactor was filled with Poraver (foam glass particles) running at anaerobic conditions and one suspended carrier biofilm reactor working aerobically. Chemical oxygen demand (COD), chloride, sulphate, pH, dissolved oxygen, total toxaphene and specific toxaphene isomers were measured. After 6 weeks approx. 87% of the total toxaphene was degraded reaching 98% by week 39. The majority of the conversion took place in the anaerobic reactor. The concentrations of toxaphene isomers with more chlorine substituents decreased more rapidly than for isomers with less chlorine substituents.     

Flood-risk management strategies for an uncertain future: living with Rhine River floods in The Netherlands?

Social pressure on alluvial plains and deltas is large, both from an economic point of view and from a nature conservation point of view. Gradually, flood risks increase with economic development, because the expected damage increases, and with higher dikes, because the flooding depth increases. Global change, changing social desires, but also changing views, require a revision of flood-risk management strategies for the long term. These should be based on resilience as opposed to the resistence strategy of heightening dikes. Resilience strategies for flood-risk management imply that the river is allowed to temporarily flood large areas, whereas the flood damage is minimized by adapting land use. Such strategies are thus based on risk management and 'living with floods' instead of on hazard control. For The Netherlands, one of the most densely populated deltas in the world, alternative resilience strategies have been elaborated and assessed for their hydraulic functioning and 'sustainability criteria'.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths <60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 x 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre(-1), six plots were mixed with sewage sludge (SS) at 15 t acre(-1), and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO3, NH4, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO3-N and NH4-N) in runoff water than SS treatments. Total marketable yield (lbs acre(-1)) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

Modulation of steroidogenesis by coastal waters and sewage effluents of Hong Kong, China, using the H295R assay

BACKGROUND, AIM, AND SCOPE: The presence of a variety of pollutants in the aquatic environment that can potentially interfere with the production of sex steroid hormones in wildlife and humans has been of increasing concern. The aim of the present study was to investigate the effects of extracts from Hong Kong marine waters, and influents and effluents from wastewater treatment plants on steroidogenesis using the H295R cell bioassay. After exposing H295R cells to extracts of water, the expression of four steroidogenic genes and the production of three steroid hormones were measured. MATERIALS AND METHODS: Water samples were collected during the summer of 2005 from 24 coastal marine areas and from the influents and effluents of two major waste water treatment plants (WWTPs) in Hong Kong, China. Samples were extracted by solid phase extraction (SPE). H295R cells were exposed for 48 h to dilutions of these extracts. Modulations of the expression of the steroidogenic genes CYP19, CYP17, 3betaHSD2, and CYP11beta2 were determined by measuring mRNA concentrations by real-time polymerase chain reaction (Q-RT-PCR). Production of the hormones progesterone (P), estradiol (E2), and testosterone (T) was quantified using enzyme linked immunosorbent assays (ELISA). RESULTS: Extracts from samples collected in two fish culture areas inhibited growth and proliferation of H295R cells at concentrations greater or equal to 10(5) L equivalents. The cells were exposed to the equivalent concentration of active substances in 10,000 L of water. Thus, to observe the same level of effect as observed in vitro on aquatic organisms would require a bioaccumulation factor of this same magnitude. None of the other 22 marine samples affected growth of the cells at any dilution tested. Twelve of the marine water samples completely inhibited the expression of CYP19 without affecting E2 production; inhibition of CYP17 expression was observed only in one of the samples while expression of CYP11beta2 was induced as much as five- and ninefold after exposure of cells to extracts from two locations. The expression of the progesterone gene 3betaHSD2 was not affected by any of the samples; only one sample induced approximately fourfold the production of E2. Although more than twofold inductions were observed for P and T production, none of these values were statistically significant to conclude effects on the production of these two hormones. While influents from WWTPs did not affect gene expression, an approximately 30% inhibition in the production of E2 and a 40% increase in P occurred for the exposure with influents from the Sha Tin and Stonecutters WWTPs, respectively. Effluents from WWTPs did not affect the production of any of the studied hormones, but a decrement in the expression of the aldosterone gene CYP11beta2 was observed for the Sha Tin WWTP exposure. No direct correlation could be established between gene expression and hormone production. DISCUSSION: Observed cytotoxicity in the two samples from fish culture areas suggest the presence of toxic compounds; chemical analysis is required for their full identification. Although effluents from WWTPs did not affect hormone production, other types of endocrine activity such as receptor-mediated effects cannot be ruled out. Interactions due to the complexity of the samples and alternative steroidogenic pathways might explain the lack of correlation between gene expression and hormone production results. CONCLUSIONS: Changes observed in gene expression and hormone production suggest the presence in Hong Kong coastal waters of pollutants with endocrine disruption potential and others of significant toxic effects. The aromatase and aldosterone genes seem to be the most affected by the exposures, while E2 and P are the hormones with more significant changes observed. Results also suggest effectiveness in the removing of compounds with endocrine activity by the WWTPs studied, as effluent samples did not significantly affect hormone production. The H295R cell showed to be a valuable toll in the battery required for the analysis of endocrine disrupting activities of complex environmental samples. RECOMMENDATIONS AND PERSPECTIVES: Due to the intrinsic complexity of environmental samples, a combination of analytical tools is required to realistically assess environmental conditions, especially in aquatic systems. In the evaluation of endocrine disrupting activities, the H295R cell bioassay should be used in combination with other genomic, biological, chemical, and hydrological tests to establish viable modes for endocrine disruption and identify compounds responsible for the observed effects.     

Comparison of nitrification rates in conventional and membrane-assisted biological nutrient removal processes

A membrane-assisted and a conventional activated sludge system, both operated in an enhanced biological phosphorus removal (EBPR) mode and under identical operating conditions, were studied to investigate the effect of the membrane solids-liquid separation on nitrification activity. Both the membrane EBPR (MEBPR) and conventional EBPR (CEBPR) processes achieved stable and complete removal of ammonium-nitrogen from the influent wastewater. However, when the intrinsic nitrification activity was assessed in offline batch tests, the CEBPR mixed liquor exhibited 15 to 75% greater nitrification potential than the MEBPR counterpart. These results were further validated by monitoring nitrification rates of conventional mixed liquor as it evolved toward a membrane mixed liquor. It was also demonstrated that the larger aerobic mass fraction of the MEBPR system could not be the only factor influencing the reduced intrinsic nitrification rate. The present study strongly suggests that the presence of a membrane solids-liquid separation per se may be sufficient to alter the nitrification kinetics of an EBPR mixed liquor and that this possibility should be considered in arriving at an appropriate process design.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.