Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater

This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.     

Polybrominated diphenyl ethers in house dust in Singapore

The use of polybrominated diphenyl ethers (PBDEs) as flame retardants in Singapore is not strictly regulated; therefore these compounds can be readily found in furniture, electronic devices, and building materials. This study was the first of its kind to be conducted in Singapore to measure concentrations of PBDEs in house dust. Samples were collected from 31 homes in various locations across the island-state of Singapore, and a total eight PBDEs congeners were measured. PBDEs were detected in all 31 dust samples and the number of BDE congener detected per home ranged between 3 and 8. The most abundant BDE congeners found were BDE 47, 99 and 209, with a median value of 20 ng g(-1) dust, 24 ng g(-1) dust and 1000 ng g(-1) dust, respectively. BDE 209 contributed 88% to the median of all the congeners, and BDE 47 and 99 contributed 1.8% and 3.5%, respectively. Different congener profiles were observed between this and studies conducted elsewhere, which is consistent with the use of different commercial PBDE around the world. No significant correlations between PBDE dust levels and residential characteristics (number of TVs and computers, floor area or flooring material) were observed. The daily intake of PBDEs via the inhalation pathway was estimated. House dust may be regarded as the most important exposure route of PBDEs for children.     

Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic)

This study assesses the status of Sacca di Goro coastal lagoon (Northern Adriatic, Italy) with respect to watershed pollution. Because 80% of its watershed is devoted to agriculture, plant protection products and their metabolites were found in the water column, sediments (the upper 0-15 cm layer), macroalgae (Ulva rigida) and clams (Tapes philippinarum). Five seasonal sampling campaigns were performed from May 2004 to April 2005 and concentrations measured in five stations in the lagoon and six in the watershed. Relatively high concentrations of the s-triazine - terbuthylazine -, urea herbicides - diuron - and alachlor were detected through the year mainly at stations directly influenced by the Po di Volano inflow. The concentrations of products in use follow a clear seasonal pattern with spring peaks. This pattern is also visible in the sediments as well as in biota. Among metabolites, hydroxylated compounds prevailed, often with concentrations greater than those of the parent compounds. For the most part of the year, the concentrations in biota were close to detection limits, with concentration peaks in spring.     

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.     

Accumulation and partitioning of heavy metals in mangroves: a synthesis of field-based studies

We report the findings of a comparative analysis examining patterns of accumulation and partitioning of the heavy metals copper (Cu), lead (Pb) and zinc (Zn) in mangroves from available field-based studies to date, employing both species level analyses and a phylogenetic approach. Despite mangroves being a taxonomically diverse group, metal accumulation and partitioning for all metals examined were broadly similar across genera and families. Patterns of metal accumulation were also similar regardless of whether species were classified as salt secreting or non-secreting. Metals were accumulated in roots to concentrations similar to those of adjacent sediments with root bio-concentration factors (BCF; ratio of root metal to sediment metal concentration) of 1< or =. Root BCFs were constant across the exposure range for all metals. Metal concentrations in leaves were half that of roots or lower. Essential metals (Cu and Zn; translocation factors (TF; ratio of leaf metal to root metal concentration) of 0.52 and 0.53, and leaf BCFs of 0.47 and 0.51, respectively) showed greater mobility than non-essential metals (Pb; TF of 0.31 and leaf BCF of 0.11). Leaf BCFs for the essential metals Cu and Zn decreased as environmental concentrations increased. The non-essential metal Pb was excluded from leaf tissue regardless of environmental concentrations. Thus mangroves as a group tend to operate as excluder species for non-essential metals and regulators of essential metals. For phytoremediation initiatives, mangrove ecosystems are perhaps best employed as phytostabilisers, potentially aiding in the retention of toxic metals and thereby reducing transport to adjacent estuarine and marine systems.     

Biodegradability and ecotoxicity of amine oxide based surfactants

The aerobic and anaerobic biodegradability as well as the aquatic toxicity of two fatty amine oxides and one fatty amido amine oxide were investigated. Aerobic biodegradation was evaluated using the CO(2) headspace test (ISO 14593) and biodegradation under anaerobic conditions was assessed employing a standardised batch test. The three amine oxide based surfactants tested were readily biodegradable under aerobic conditions but only the alkyl amido amine oxide was found to be easily biodegradable under anaerobic conditions. Toxicity to Photobacterium phosphoreum and Daphnia magna was evaluated. Bacteria (EC(50) from 0.11 to 11 mg l(-1)) proved to be more sensitive to the toxic effects of the amine oxide based surfactants than crustacea (IC(50) from 6.8 to 45 mg l(-1)). The fatty amido amine oxide showed the lowest aquatic toxicity.     

How Plants Cope with Foreign Compounds. Translocation of xenobiotic glutathione conjugates in roots of barley (Hordeum vulgare) (9 pp)

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.     

Endpoint ‘floating leaves’ of <Emphasis Type="Italic">Potamogeton natans</Emphasis>: A new method to evaluate the development of macrophytes in pond mesocosms

Goal, Scope and Background One of the advantages of long-term mesocosm experiments as compared to short-term standard toxicity tests in the laboratory is the potential for detecting secondary effects due to the interaction of species and recovery with biomass of macrophytes being an important endpoint. However, generating biomass data by harvesting is often laborious, time-consuming, costly and restricted to the end of the experiment. Moreover, valuable information may get lost, in particular in single application studies, since maximal primary effects and secondary effects or recovery occur per se at different times. Potamogeton natans was used as an example in order to test whether number and area of floating leaves can be reliably measured and be used as intermediate and final endpoints in mesocosm effect studies. Methods Digital photos, which were taken of the water surface in the course of an indoor pond mesocosm study on herbicide effects, were subjected to image analysis. The results were compared to wet weight and ash-free dry weight of Potamogeton at the end of the herbicide study. Results and Discussion Both number and area of floating leaves indicated the same herbicide effects as wet weight and ash-free dry weight of Potamogeton. Error introduced by the different work steps is small and can be further minimised by a number of method improvements. Recommendations and Perspectives In indoor mesocosm studies, errors due to the perspective adjustment may be circumvented by taking the photos perpendicular to the water surface. Correction for lens aberration, identical light conditions and the use of fluorescence images are considered promising. Field applications are proposed.     

A study of climate change and anthropogenic impacts in West Africa

BACKGROUND, AIM AND SCOPE: During the last decades ecological conditions in West Africa have dramatically changed. Very evident is the climate change, which has resulted in a southward shift of the climate zones, e.g. a spread of the desert (Sahara) into the Sahelian zone. After the drought period of the early 1970s and 1980s, livestock density increased resulting in an intensification of grazing pressure. This anthropogenous phenomenon leads to similar landscape changes as those caused by the climate. Only very few investigations exist on vegetation dynamics, climate changes and land use changes for the Sudanian zone. The paper presents data on changes of precipitation, of land use, of the geographical range of species, and of the composition of the flora, which have to be regarded as proofs of the sahelisation of large areas of the Sudanian zone. MATERIALS AND METHODS: Area of investigation: Burkina Faso. Precipitation data analysis: precipitation data from 67 stations; time series analysis and geo-statistical spatial interpolation. Analysis of land use change: Landsat satellite MSS and ETM+ data, acquired for two different dates between 1972 and 2001 analyzed by the software ERDAS/IMAGINE version 8.6 and ArcView 3.2 with the Spatial Analyst extension. Intensive ground truthing (160 training areas). Inventory of the flora: based on the data of the Herbarium Senckenbergianum (FR) in Frankfurt, Germany, and of the herbarium of the university of Ouagadougou (OUA), Burkina Faso, as well as on various investigations on the vegetation of Burkina Faso carried out in the years 1990 to 2005 by the team of the senior author. Life form analysis of the flora: based on the inventory of permanent plots. RESULTS AND DISCUSSION: Precipitation: Remarkable latitudinal shift of isohyets towards the South translates to a general reduction of average rainfall in great parts of the country. The last decade (1990-1999) shows some improvement, however, the more humid conditions of the 1950's and 1960's are not yet established again. Landcover change: In the study region the extent of arable fields and young fallows increased during the last 30 years from 580 km(2) in 1972 to 2870 km(2) in 2001. This means an average land cover conversion rate of 0.9% per year for the 6 departments considered. Change of the distribution of Sahelian and Sudanian species: Several species, mentioned in older literature as strictly Sahelian, today also occur in the Sudanian zone. Parallel to the spread of former strictly Sahelian species into the Sudanian zone, some former Sahelo-Sudanian species have withdrawn from the Sahel. Changes of the life form spectra of the flora: Considering their life form spectra, the flora of heavily grazed and of protected areas in the Sudanian zone show great differences. On areas intensively grazed the percentage of therophytes is evidently higher than on protected areas. Just the opposite is true for the phanerophytes. Their percentage is higher on the protected area than on the grazed zones. At the first glance, it is obvious to link the changes in flora and vegetation with the climate changes that have occurred during the last five decades (decrease of annual precipitation). However, not only climatic conditions have changed, but also population has increased, the percentage of land intensively used for agriculture and pasturing has increased and the time for soil regeneration today is much shorter than it was some decades ago. Thus, the landscape of the Sudanian zone has become a more Sahelian character. A comparison of the flora of an intensively used area of the Sudanian zone with that of a protected area shows a remarkable change in the life form spectra. The spectrum of the intensively used area is almost identical with that of the typical Sahelian flora. This comparison shows that the anthropogenic influence plays a greater role in the sahelisation of the Sudanian zone than the climate change. CONCLUSION: Climate change and anthropogenic influence both, lead to a sahelisation of landscape and flora. Thus in many parts of the Sudanian zone of West Africa sahelisation phenomena will remain and even increase independently from the reestablishment of the more humid climate conditions of the 1950ies. RECOMMENDATIONS AND PERSPECTIVES: In order to maintain some parts of the characteristic Sudanian landscape with its characteristic flora and vegetation, the number and size of protected areas should be augmented. For all protected areas it has to be ensured, that protection is reality, i.e. respected an understood by local people, not only fiction. As long as the enlargement of intensively used areas continues the sahelisation of flora, vegetation and landscape will continue too.