Surveillance programme on dioxin levels in soils in the Campo de Gibraltar (southwest Spain)

The results of an epidemiologic study undertaken by the Spanish Council for Scientific Research (CSIC) after commission by the Spanish Parliament indicated that Huelva and Cádiz were the zones in Andalusia with elevated risk of cancer. A 6% (women) and 10% (men) cancer mortality excess was observed with respect to the other six Andalusian provinces. Huelva and Cádiz are located in the south-western region of Spain, and are characterized by a strong industrial activity concentrated in several industrial sites. This situation led to two environmental surveys in these areas, in which the presence of dioxins was studied among other parameters. A PCDD/F assessment in soils of the Campo de Gibraltar (Cádiz) was carried out from June 2003 to June 2004. A total of 20 samples were collected in this study divided in two sampling campaigns. The first 10 samples were taken in locations affected by high industrial activity zones as well as in landfills (hotspots). The rest of the samples were collected in areas that were not expected to be contaminated, such as agricultural zones and forests. I-TEQ values of the samples ranged from 0.26 to 15.08 ng/kg dm. In all, 85% of the samples were below the limit of 5 ng I-TEQ/kg I-TEQ concentrations of three samples only surpassed this limit. These zones corresponded to a landfill, a quarry used for dumping chemical product containers and a sample from the sewage system of the industrial site. These sites were used neither for agricultural nor for public purposes.     

Heavy metal bioavailability and effects: II. Histopathology-bioaccumulation relationships caused by mining activities in the Gulf of Cádiz (SW, Spain)

The relationship between bioaccumulation of heavy metals (Zn, Cd, Pb and Cu) and histological lesions in different tissues of organisms is assessed in three different areas located in the southwest of Spain in the Gulf of Cádiz (Ría of Huelva, Guadalquivir estuary and Bay of Cádiz) affected and non-affected by mining activities. Data included in these relationships were obtained along the years 2000 and 2001 to address the impact of the Aznalcóllar mining spill on the Guadalquivir estuary. The bioaccumulation and the histological lesions measured in this seasonal study in the Gudalquivir estuary were linked to derive tissue quality guidelines (TQGs) by means of a multivariate analysis approach (MAA). Sediments collected in the same areas of study were used to expose organisms during the survey carried out in autumn 2001 and to address the relationship between bioaccumulation and histological lesions under laboratory conditions and related to chemicals bound to sediments. Lesions show that the organisms collected in the ría of Huelva and exposed to their sediments were severe, intermediate in the Guadalquivir estuary and absent in the Bay of Cádiz. Results show that the Guadalquivir estuary trends to recover its initial status quo previous to the mining spill. The link between chemical concentration and the lesions measured in the same tissues using MAA permits to derive tissue quality guidelines for two organisms, oysters (Crassostrea angulata) and clams (Scrobicularia plana) collected in the Guadalquivir estuary and associated with the heavy metals from the mining spill (Zn and Cd). The TQG values expressed as concentrations (mgkg-1--dry weight) not associated with biological effects are for oysters, Zn, 8603, Cd, 3.42; and for clams Zn, 800, Cd, 2.6.     

Accumulation and histopathological damage in the clam Ruditapes philippinarum and the crab Carcinus maenas to assess sediment toxicity in Spanish ports

The degree of contamination and toxicity in sediment from four Spanish ports (Cádiz, Huelva, Pasajes and Bilbao) was assessed in the present study. Two marine invertebrate species, the shore crab Carcinus maenas and the clam Ruditapes philippinarum, were exposed to the different sediments under laboratory conditions for 28 days. Relationships were developed among metal contamination (As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in sediments, metal accumulation in gill tissues and histopathological lesions in different biological tissues to assess sediment toxicity. A multivariate analysis approach was used to calculate sediment quality guidelines (SQGs) by linking metal concentration in sediments with histopathological lesions measured in the exposed organisms. The results showed significant contaminant accumulation and histopathological lesions due to As, Pb and Zn in sediments at the port of Huelva; As, Cr, Cu, Hg and Ni at the ports of Pasajes and Cádiz; and Cr and Hg at the port of Bilbao. The link between chemical concentration in sediments and histopathological lesions allowed the determination of SQGs for the chemicals As, Cd, Cu, Cr, Hg, Ni and Zn.     

Heavy metal bioavailability and effects: I. Bioaccumulation caused by mining activities in the Gulf of Cádiz (SW, Spain)

The bioaccumulation of six metals (Fe, Mn, Zn, Cd, Pb and Cu) was studied as part of the monitoring of the Aznalcóllar mining spill (April 1998) on the Guadalquivir estuary and in other estuaries located in the Gulf of Cádiz. Fish, clams and oysters were collected during different seasonal periods along the years 2000 and 2001 in the Guadalquivir estuary to determine the bioaccumulation of the metals originated by the mining spill. Results were compared to the bioaccumulation of the same metals in fish and clams exposed in the laboratory to sediments collected in the same areas during autumn 2001. The bioaccumulation of these metals was compared to the concentration of metals measured in tissues of same taxas collected in the areas of the ria of Huelva and the Bay of Cádiz. Results show that the bioaccumulation of Zn and Cd in the organisms sampled in the Guadalquivir estuary was associated with the enrichment of these metals in the estuary from the mining spill and decreased along the time reaching the lowest values in autumn 2001. The metal Cu show different trends that are associated with other sources of contamination than the spill and related to the transport of this metal from Huelva to Guadalquivir estuary and/or to the use of this metal as plaguicide in the rice fields located in the area. The comparison between bioaccumulation results under field and laboratory conditions obtained in the different areas of study shows that these data can be used to discriminate between acute and chronic impacts associated with mining activities.     

Temporal evolution of polycyclic aromatic hydrocarbons (PAHs) in sludge from wastewater treatment plants: comparison between PAHs and heavy metals

This paper presents results on the presence and temporal variability of the 16 PAHs recommended by the EPA in primary, secondary and digested sewage sludge over a year. The sewage sludges originated from the Guadalete wastewater treatment plant (WWTP) site in Jerez de la Frontera (Cádiz, Spain). These organic pollutants have been extracted from the sewage sludge by microwave energy. High performance liquid chromatography coupled with diode array (HPLC-DAD) or fluorescence (HPLC-FL) detectors have been used. The results showed that total PAHs concentration varied between 1,945 ng g(-1) dry matter (DM) for primary sludges collected in March and 10,100 ng g(-1) DM for primary sludge collected in June. Generally, concentrations of PAHs were higher in compost and digested sludge than in fresh one. On the other hand, the highest concentration of PAHs were found on summer. This thing is associated to the traffic increase from inland zones to the coast (Jerez de la Frontera is very near to beaches). Finally, this paper present a comparative study of the American an European legislation concluding that the limits of concentrations established are not exceeded. In addition heavy metals were analysed. The origin of PAHs and heavy metals seems to be different.     

Dating of marine sediments and time evolution of heavy metal concentrations in the Bay of Cádiz, Spain

In this paper the time evolution of heavy metal concentration of Pb, Zn, Cd and Hg, in the sediments of the Bay of Cádiz (southwest of Spain) is studied during the past century, as a result of the industrial influence in the zone. The study has been performed using sedimentary profiles that have been extracted from the seabed. The measurement of 210Pb and 137Cs radionuclides has provided the dating of the sediment layers, up to a depth corresponding to the age of 115 years. The relative sedimentation rates obtained are around 0.2 cm/year. The 137Cs activity profile reflects the concentration of this radionuclide in the atmosphere and into aquatic systems during the second half of the twentieth century. This profile has been used to ratify the results provided by the 210Pb dating method.     

Comparing sediment quality in Spanish littoral areas affected by acute (Prestige, 2002) and chronic (Bay of Algeciras) oil spills

The quality of sediments collected from two areas of the Spanish coast affected by different sources of contaminants has been compared in this study. The areas studied are the coast of Galicia affected by the oil spill from the tanker Prestige (November 2002) and the Gulf of Cádiz which suffers continuous inputs of contaminants from industries located in the area and from oil spills. Contamination by several chemicals (metals, PCBs and PAHs) that bind to sediments was analyzed, and two toxicity tests (Microtox) and amphipod 10-day bioassay) were conducted. PAHs were identified as the compounds responsible for the toxic effects. Results show differences between an acute impact related to the sinking of the tanker Prestige and the chronic impact associated with continuous oil spills associated with the maritime and industrial activities in the Bay of Algeciras, this being the most polluted part of the two coastal areas studied in this work.     

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.     

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes

Purpose

Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal.

Methods

The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12?h corresponding to food-to-mass ratios varying in the range of 0.2?C0.7?mg chemical oxygen demand (COD) mg^?1 volatile suspended solids day^?1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics.

Results

The results showed that the lowering of HRT below 24?h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R ² (>0.95). The Grau second-order substrate removal constant (K ₂) was calculated as 1.12 and 7.53?day^?1 for reactors R2 and R3, respectively.

Conclusion

This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

Estimates of atmospheric particle emissions from bulk handling of dusty materials in Spanish Harbours

The objective of this paper is to show the methodology developed to estimate particle emissions from several typical activities of bulk handling in harbours. It is based on several field experiments carried out in the Harbour of Tarragona, where high time resolution monitors were deployed close to different areas of bulk solids handling operations. Monitors recorded particle concentrations and meteorological variables. A high-resolution dispersion model is used to estimate the emission rates that best fits the observations. Results were comparable to those obtained with the AP-42 (EPA). The new emission estimates are used as input for an emission model called EMIPORT. The model also employs AP-42 (EPA) emission factors as a complement. This work is one of the activities of the LIFE project called HADA (Herramienta Automática de Diagnóstico Ambiental or in English Automatic Tool for Environmental Diagnostic).     

Illumina sequencing-based analysis of a microbial community enriched under anaerobic methane oxidation condition coupled to denitrification revealed coexistence of aerobic and anaerobic methanotrophs

Methane is produced in anaerobic environments, such as reactors used to treat wastewaters, and can be consumed by methanotrophs. The composition and structure of a microbial community enriched from anaerobic sewage sludge under methane-oxidation condition coupled to denitrification were investigated. Denaturing gradient gel electrophoresis (DGGE) analysis retrieved sequences of Methylocaldum and Chloroflexi. Deep sequencing analysis revealed a complex community that changed over time and was affected by methane concentration. Methylocaldum (8.2%), Methylosinus (2.3%), Methylomonas (0.02%), Methylacidiphilales (0.45%), Nitrospirales (0.18%), and Methanosarcinales (0.3%) were detected. Despite denitrifying conditions provided, Nitrospirales and Methanosarcinales, known to perform anaerobic methane oxidation coupled to denitrification (DAMO) process, were in very low abundance. Results demonstrated that aerobic and anaerobic methanotrophs coexisted in the reactor together with heterotrophic microorganisms, suggesting that a diverse microbial community was important to sustain methanotrophic activity. The methanogenic sludge was a good inoculum to enrich methanotrophs, and cultivation conditions play a selective role in determining community composition.     

Harnessing dark fermentative hydrogen from pretreated mixture of food waste and sewage sludge under sequencing batch mode

Food waste and sewage sludge are the most abundant and problematic organic wastes in any society. Mixture of these two wastes may provide appropriate substrate condition for dark fermentative biohydrogen production based on synergistic mutual benefits. This work evaluates continuous hydrogen production from the cosubstrate of food waste and sewage sludge to verify mechanisms of performance improvement in anaerobic sequencing batch reactors. Volatile solid concentration and mixing ratio of food waste and sludge were adjusted to 5 % and 80:20, respectively. Five different hydraulic retention times (HRT) of 36, 42, 48, 72, and 108 h were tested using anaerobic sequencing batch reactors to find out optimal operating condition. Results show that the best performance was achieved at HRT 72 h, where the hydrogen yield, the hydrogen production rate, and hydrogen content were 62.0 mL H₂/g VS, 1.0 L H₂/L/day, and ~50 %, respectively. Sufficient solid retention time (143 h) and proper loading rate (8.2 g COD/L/day as carbohydrate) at HRT 72h led to the enhanced performance with better hydrogen production showing appropriate n-butyrate/acetate (B/A) ratio of 2.6. Analytical result of terminal-restriction fragment length polymorphism revealed that specific peaks associated with Clostridium sp. and Bacillus sp. were strongly related to enhanced hydrogen production from the cosubstrate of food waste and sewage sludge.     

Induced cytochrome P450 1A activity in cichlid fishes from Guandu River and Jacarepaguá Lake, Rio de Janeiro, Brazil

The induction of cytochrome P4501A-mediated activity (e.g. ethoxyresorufin-O-deethylation, EROD) has been used as a biomarker for monitoring fish exposure to AhR-receptor ligands such as polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and polychlorinated dibenzo-dioxins/furans (PCDD/Fs). In this study we found that hepatic EROD is induced in fish ("Nile tilapia", Oreochromis niloticus and "acará", Geophagus brasiliensis) from the Guandu River (7-17-fold) and Jacarepaguá Lake (7-fold), Rio de Janeiro, Brazil. Since both cichlid fish are consumed by the local population and the Guandu River is the main source of the drinking water supply for the greater Rio de Janeiro metropolitan area, pollution by cytochrome P4501A-inducing chemicals is a cause for concern and should be further investigated in sediments, water and biota. We additionally showed that EROD activity in the fish liver post-mitochondrial supernatant-simpler, cheaper and less time consuming to prepare than the microsomal fraction-is sufficiently sensitive for monitoring purposes.     

Development of a United States-Mexico Emissions Inventory for the Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was commissioned to investigate the sources of haze at Big Bend National Park in southwest Texas. The modeling domain of the BRAVO Study includes most of the continental United States and Mexico. The BRAVO emissions inventory was constructed from the 1999 National Emission Inventory for the United States, modified to include finer-resolution data for Texas and 13 U.S. states in close proximity. The first regional-scale Mexican emissions inventory designed for air-quality modeling applications was developed for 10 northern Mexican states, the Tula Industrial Park in the state of Hidalgo, and the Popocatépetl volcano in the state of Puebla. Emissions data were compiled from numerous sources, including the U.S. Environmental Protection Agency (EPA), the Texas Natural Resources Conservation Commission (now Texas Commission on Environmental Quality), the Eastern Research Group, the Minerals Management Service, the Instituto Nacional de Ecología, and the Instituto Nacional de Estadistica Geografía y Informática. The inventory includes emissions for CO, nitrogen oxides, sulfur dioxide, volatile organic compounds (VOCs), ammonia, particulate matter (PM) < 10 microm in aerodynamic diameter, and PM < 2.5 microm in aerodynamic diameter. Wind-blown dust and biomass burning were not included in the inventory, although high concentrations of dust and organic PM attributed to biomass burning have been observed at Big Bend National Park. The SMOKE modeling system was used to generate gridded emissions fields for use with the Regional Modeling System for Aerosols and Deposition (REMSAD) and the Community Multiscale Air Quality model modified with the Model of Aerosol Dynamics, Reaction, Ionization and Dissolution (CMAQ-MADRID). The compilation of the inventory, supporting model input data, and issues encountered during the development of the inventory are documented. A comparison of the BRAVO emissions inventory for Mexico with other emerging Mexican emission inventories illustrates their uncertainty.     

Transport and degradation of propylene glycol in the vadose zone: model development and sensitivity analysis

Transport and degradation of de-icing chemical (containing propylene glycol, PG) in the vadose zone were studied with a lysimeter experiment and a model, in which transient water flow, kinetic degradation of PG and soil chemistry were combined. The lysimeter experiment indicated that aerobic as well as anaerobic degradation occurs in the vadose zone. Therefore, the model included both types of degradation, which was made possible by assuming advection-controlled (mobile) and diffusion-controlled (immobile) zones. In the mobile zone, oxygen can be transported by diffusion in the gas phase. The immobile zone is always water-saturated, and oxygen only diffuses slowly in the water phase. Therefore, the model is designed in a way that the redox potential can decrease when PG is degraded, and thus, anaerobic degradation can occur. In our model, manganese oxide (MnO₂, which is present in the soil) and NO \(_{3}^{-}\) (applied to enhance biodegradation) can be used as electron acceptors for anaerobic degradation. The application of NO \(_{3}^{-}\) does not result in a lower leaching of PG nor in a slower depletion of MnO₂. The thickness of the snowcover influences the leached fraction of PG, as with a high infiltration rate, transport is fast, there is less time for degradation and thus more PG will leach. The model showed that, in this soil, the effect of the water flow dominates over the effect of the degradation parameters on the leaching at a 1-m depth.     

Effects of aeration frequency on leachate quality and waste in simulated hybrid bioreactor landfills

Research has been conducted to investigate the effects of daily aeration frequency on leachate quality and waste settlement in simulated hybrid landfill bioreactors. Four laboratory-scale reactors were constructed and operated for about 10 months to simulate different bioreactor operations, including one anaerobic bioreactor and three hybrid bioreactors with different aeration frequencies (one, two, and four times per day). Chemical oxygen demand (COD) and biochemical oxygen demand (BOD₅) reduced more than 96% of the initial concentrations in all aerated bioreactors. The differences of COD and BOD₅ reductions among tested aeration frequencies were relatively small. For ammonia nitrogen, the higher aeration frequency (two or four times per day) resulted in the quicker reduction. Overall, the concentrations of heavy metals (Cr, Co, Cu, Mn, Ni, and Zn) decreased over time except Cd and Pb. The reduction of redox-sensitive metal concentrations (Mn, Co, Ni, and Cu) was greater in aerated bioreactors than in anaerobic bioreactor. Settlement of municipal solid waste (MSW) was enhanced with higher frequency of aeration events (four times per day).

Implications: In recent years, hybird bioreactor landfill technology has gained a lot of attention. Appropriate aeration rate is crucial for hybrid bioreactor operation, but few studies have been done and different results were obtained. Research was conducted to investigate the effects of daily aeration frequency on leachate quality and waste settlement. Results indicated that aeration can effectively accelerate waste stabilization and remove organic carbon concentration and total nitrogen in the leachate.     

Improved computational model (AQUIFAS) for activated sludge, integrated fixed-film activated sludge, and moving-bed biofilm reactor systems, Part I: Semi-empirical model development

Research was undertaken to develop a model for activated sludge, integrated fixed-film activated sludge (IFAS), and moving-bed biofilm reactor (MBBR) systems. The model can operate with up to 12 cells (reactors) in series, with biofilm media incorporated to one or more cells, except the anaerobic cells. The process configuration can be any combination of anaerobic, anoxic, aerobic, post-anoxic with or without supplemental carbon, and reaeration; it can also include any combination of step feed and recycles, including recycles for mixed liquor, return activated sludge, nitrates, and membrane bioreactors. This paper presents the structure of the model. The model embeds a biofilm model into a multicell activated sludge model. The biofilm flux rates for organics, nutrients, and biomass can be computed by two methods--a semi-empirical model of the biofilm that is relatively simpler, or a diffusional model that is computationally intensive. The values of the kinetic parameters for the model were measured using pilot-scale activated sludge, IFAS, and MBBR systems. For the semiempirical version, a series of Monod equations were developed for chemical oxygen demand, ammonium-nitrogen, and oxidized-nitrogen fluxes to the biofilm. Within the equations, a second Monod expression is used to simulate the effect of changes in biofilm thickness and fraction nitrifiers in the biofilm. The biofilm flux model is then linked to the activated sludge model. The diffusional model and the verification of the models are presented in subsequent papers (Sen and Randall, 2008a, 2008b). The model can be used to quantify the amount of media and surface area required to achieve nitrification, identify the best locations for the media, and optimize the dissolved oxygen levels and nitrate recycle rates. Some of the advanced features include the ability to apply different media types and fill fractions in cells; quantify nitrification, denitrification, and biomass production in the biofilm and mixed liquor suspended solids; and perform dynamic simulations.     

Changes in toxicity and genotoxicity of industrial sewage sludge samples containing nitro- and amino-aromatic compounds following treatment in bioreactors with different oxygen regimes

Goals, Scope and Background

From 2005, deposition of organic waste will be banned in Sweden. Likewise, in Germany and Austria, similar bans are being planned, and further countries will probably follow. Thus, there is a need to develop new methods and to refine established techniques for sludge management in the whole of the European Union. For this end, there is also an urgent need for appropriate ecotoxicological approaches to elucidate and assess the hazard potential of sewage sludge. Therefore, the present study was designed to assess the capacity of various established sludge treatment methods using different oxygen regimes to degrade recalcitrant nitro-substituted organic compounds and reduce their toxicity. Sewage sludge samples from a wastewater treatment plant in Sweden (Cambrex Karlskoga AB, industrial area Björkborn) receiving wastewater from industries manufacturing pharmaceutical substances, chemical intermediates and explosives were processed with different sludge treatment methods. Among other treatment methods, bioreactors (for anaerobic and aerobic sludge treatment) were used. In the present investigation, a battery ofin vitro bioassays was employed to compare the cytotoxic and genotoxic potentials of different fractions of sludge samples in order to elucidate whether the treatments were suitable to reduce the toxicity of the sludge.

Methods

In order to investigate the cytotoxicity of the extracts of treated and untreated sludge samples, the acute cytotoxicity test with the permanent cell line RTL-W1 was used. Genotoxicity was tested by means of the comet assay (single cell gel electro-phoresis) with RTL-W1cells, and mutagenicity was assessed with the Ames test using the Salmonella typhimurium strains TA98, TA98NR and TA100. Sludge toxicity was tested in different fractions of organic extracts produced by acetone and hexane extractions. The subsequent clean-up procedure (silica gel chro-matography and elution with hexane and dichloromethane) resulted in two fractions, a lipophilic hexane-fraction and a semi-lipophilic dichloromethane-fraction. For the genotoxicity and mutagenicity tests, these fractions were reunited at equal ratios.

Results and Discussion

The acute cytotoxicity test with RTL-Wl cells revealed a high cytotoxic potential for the semi-li-pophilic DM-fractions of all sludge samples with NR₅₀ values (= effective concentration for 50% cell death in the neutral red test) from 8.9 up to 20 mg sludge d.w./ml medium. A low cytotoxic potential for the hexane fractions of the untreated sludge samples (NR₅₀ 400 to < 400 mg sludge d.w./ml medium) was observed, whereas the hexane fractions of the treated sludge samples showed elevated cytotoxicity increasing further with treatment in the bioreactors. The comet assay indicated that three out of eight of the reunited fractions had a significant genotoxic potential. Whereas the genotoxic potential of one sample treated anaerobically was very high with an induction factor of 11.6, a similar sample (taken from the same anaerobic reactor four months later) and one untreated sample showed lower potentials. The samples treated in another anaerobic bioreactor as well as the samples treated aerobically showed no genotoxic potential. Results indicate that aerobic treatment was basically adequate for reducing the genotoxicity of the sludge, whereas anaerobic treatment was only partly useful for reduction of genotoxicity. The Ames test revealed a very high mutagenic potential for the reunited fractions of the untreated sludge samples with strain TA98 (maximum induction factors (IF_max up to 45) and a relatively high potential for one of the samples treated aerobically (S2, IF_max = 18 (TA98, S9-)), thus documenting the suitability of both anaerobic and aerobic treatments to reduce the mutagenicity of the samples, however, with the aerobic treatment being less effective. Conclusions. Overall, none of the microbiological treatments for wastewater sludge in bioreactors was found to be ideal for general toxicity reduction of the sludge samples. Whereas cytotoxicity of the sludge increased or levelled off in most cases following either treatment, genotoxicity both increased or decreased after anaerobic treatment, depending on the specific sample. However, mutagenicity could generally be reduced by anaerobic treatment and, to a lesser degree, by aerobic treatment. Recommendationsand Perspectives. The complex modification of the diverse damage potentials of sludge sample extracts by use of anin vitro biotest battery following treatment for toxicity reduction in bioreactors showed that considerations of different toxicological endpoints is essential for an adequate hazard assessment. Whereas in the case of cytotoxicity reduction, the reactors proved ineffective, mutagenicity could be reduced significantly at least in some cases in this case study.

     

Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies

Background, aim, scope

Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst.

Materials and methods

Ferrous sulfate (FeSO₄·7H₂O), sulfuric acid (36?N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50?cm and diameter 6?cm, were fabricated with PVC while one reactor was packed with MAC of mass 150?g and other without MAC served as control.

Results and discussion

The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89?kJ/mol, respectively. The thermodynamic parameters ??G, ??H, and ??S were calculated for the oxidation processes using Van??t Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV?Cvisible spectroscopy, and cyclic voltammetry.

Conclusions

The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time?C4?h, and H₂O₂/FeSO₄·7H₂O in the molar ratio of 2:1.