Field validation of specific ecotoxicological tools for aquatic systems impacted with acid mine drainage

Acid mine drainage (AMD) is characterised by very low pH and high heavy metal concentrations. Serious ecotoxicological effects, often leading to the complete disruption of the ecosystem, can be observed at the regions suffering this kind of contamination. Those effects can be caused either by low pH itself or by other contaminants that emerge with water acidification (mobilisation and increased solubility of heavy metals). The discrimination between the toxicity due to each of these two factors is not possible with the existing toxicity tests; the addition of chelating agents or serial dilution methods seriously alter the chemical and physical properties of the effluent. A toxicity test, based on the survival time of Ceriodaphnia dubia (Crustacea, Cladocera) neonates exposed to the unchanged effluent, was developed and field validated, on an AMD contaminated site.     

Bench-scale assessment of combustion toxicity—A critical analysis of current protocols

The toxicity of fire effluents is not a material property but a function of both the material and the fire environment. To be meaningful, it is essential that toxicity results should relate to the end-use fire situation. This paper reviews current fire effluent toxicity tests, their relevance to fire, and the ways of assessing and applying their results to reduce fire hazards. There are a large number of different methods for determination of the toxic potency of fire effluents from materials or products. These different methods yield apparently inconsistent data because they represent different fire scenarios; measure product yields either as a function of material flammability or independent of it; base the toxicity assessment on the concentrations of different species; or use animal exposure to generate an overall estimate of toxic potency without knowledge of the relative contributions of the chemical species.     

On-Line Toxicity Monitoring Using Amtox

As environmental legislation around the world becomes more stringent, it is vital that biological systems are able to treat the effluents which are discharged from wastewater-treatment plants. Conventional treatment such as BOD removal has been achieved successfully for many years, but the requirements for toxicity removal are more onerous. The Amtox system, which was designed to give operators of wastewater-treatment plants a tool for assessing the toxicity/treatability, uses an immobilized culture of nitrifying bacteria, maintained in a heated aerobic reactor, to determine whether or not a waste is degradable. The system has a broad range of applications from treatability tests to process monitoring and toxicity tracing and, by changing the culture, effluent toxicity monitoring.
This paper details two case studies: (i) in an abattoir where an Amtox monitor was used to diagnose the source of toxicity, and (ii) on the River Trent.     

A novel hybrid nano zerovalent iron initiated oxidation--biological degradation approach for remediation of recalcitrant waste metalworking fluids

Disposal of operationally exhausted metal working fluids (MWF) through a biological route is an attractive option, since it is effective with relatively low energy demands. However, it is enormously challenging since these fluids are chemically complex, including the addition of toxic biocides which are added specifically to retard bio-deterioration whilst the fluids are operational. Nano-sized elemental iron represents a new generation of environmental remediation technologies. Laboratory scale batch studies were performed to test the degradation ability of a semi-synthetic metalworking fluid (MWF) wastewater (which was found to be resistant to initial bacterial treatment in specifically established bioreactors) by employing a novel hybrid approach. The approach was to combine the synergistic effects of nano zerovalent iron (nZVI) induced oxidation, followed by biodegradation, specifically for the remediation of recalcitrant components of MWF effluent. Addition of nZVI particles to oxygenated wastewater resulted in oxidation of organic contaminants present. Our studies confirmed 78% reduction in chemical oxygen demand (COD) by nZVI oxidation at pH 3.0 and 67% reduction in neutral pH (7.5), and 85% concurrent reduction in toxicity. Importantly, this low toxicity made the nZVI treated effluent more amenable for a second stage biological oxidation step. An overall COD reduction of 95.5% was achieved by the novel combined treatment described, demonstrating that nZVI oxidation can be exploited for enhancing the biodegradability of a recalcitrant wastewater in treatment processes.     

The effectiveness of a biological treatment with Rhizopus oryzae and of a photo-Fenton oxidation in the mitigation of toxicity of a bleached kraft pulp mill effluent

Huge efforts have been made both in adopting more environmental-friendly bleaching processes, and in developing advanced oxidation processes and more effective biological treatments for the reduction of deleterious impacts of paper mill effluents. Even so, the success of such treatments is frequently reported in terms of chemical parameters without a proper evaluation of the effluent's toxicity mitigation. This is the first study reporting an exhaustive evaluation of the toxicity of a secondary bleached kraft pulp mill effluent, after either tertiary treatment with the soft-rot fungi Rhizopus oryzae or with a photo-Fenton oxidation, using a battery of freshwater species. As it has been reported the photo-Fenton/UV treatment has proved to be the most effective in reducing the colour and the COD (chemical oxygen demand) of the effluent. Nevertheless, extremely low EC₅₀ values were reported for almost all species, after this tertiary treatment. The treatment with R. oryzae was less effective in terms of colour removal and COD reduction, but proved to be the most promising in reducing toxicity.     

Detoxification of kraft pulp ECF bleaching effluents by catalytic hydrotreatment

Two different effluents from the D(1) and E(1) stages of the ECF bleaching of Eucalyptus globulus kraft pulp were treated by catalytic hydrogenation in a trickle bed reactor using commercial and homemade Pd/AC catalysts. The reactor was fed with the bleaching effluent and a H(2)/N(2) gas stream. The variables studied were space-time (1.4-5g(cat)min/mL), gas to liquid flow ratio (286-1000vol.), gas feed concentration (H(2):N(2), 1:1-1:7.3vol.), temperature (25-100 degrees C) and pressure (1-11bar). Hydrotreatment performance was evaluated in terms of ecotoxicity, adsorbable organic halogen (AOX), chemical oxygen demand (COD), biological oxygen demand (BOD(5)) and colour removal. In all the runs, the ecotoxicity of the effluents decreased as a result of the treatment, achieving reductions that ranged from 70% to 98%. Simultaneously to the reduction of toxicity, the hydrotreatment led to a decrease of the colour of the effluents, being the decrease significantly higher in the case of E(1) effluent. The AOX content was reduced by 85% and 23% for E(1) and D(1) effluents, respectively. In the case of D(1) effluent the removal of ecotoxicity was significantly higher than that of AOX, which indicates that much of the toxicity of the effluent must be associated to non-chlorinated organics. In spite of the important reduction of ecotoxicity, the biodegradability of the effluents only increased slightly. The homemade catalysts, prepared from activated carbons with a high external or non-microporous surface area and mesopore volume and a convenient surface chemistry showed a higher efficiency than the commercial one.     

Quantifying the uncertainty of on-line sensors at WWTPs during field operation

It remains an ongoing task to quantify the uncertainty of continuous measuring systems at WWTPs during field operation. The commonly used methods are based on lab experiments under standardized conditions and are only suitable for characterizing the measuring device itself. For measuring devices under field conditions, a knowledge of the response time, trueness and precision is equally important.

A method is proposed which can be used to characterize newly installed on-line sensors or to evaluate monitoring data which may contain systematic errors. The concept is based on comparative measurements between the sensor and a reference. A linear regression is used to differentiate between trueness and precision. Various statistical tests are conducted to validate the preconditions of linear regression. The information about the trueness and precision of the measuring system under field conditions helps to adapt control strategies more effectively to the relevant processes and permits sophisticated control concepts. Moreover, the concept can help to define guidelines for evaluating the uncertainties of effluent quality monitoring to overcome the concerns about on-line sensors, improve the trust in these systems and to allow the use of continuously measuring systems for legislative purposes.

The approach is discussed in detail in this paper and all statistical tests and formulas are listed in the Appendix.     

Disinfection of advanced wastewater treatment effluent by chlorine, chlorine dioxide and ozone: Experiments using seeded poliovirus

Chlorine, chlorine dioxide and ozone were tested as chemical disinfectants against seeded poliovirus and naturally-occurring fecal coliform organisms in wastewater effluent that had received secondary treatment followed by bench scale advanced wastewater treatment (AWT). The AWT sequence consisted of chemical treatment with lime or alum followed by mixed media filtration. The resulting effluent had low suspended solids concentrations but chemical oxygen demand and nitrogen concentrations only slightly lower than those of secondary effluent. Lime treatment produced greater reductions than alum treatment in virus numbers, but not in fecal coliform organisms.

With both chlorine and chlorine dioxide, in order to reduce seeded poliovirus to less than detectable levels, it was necessary to use doses comparable to those required to disinfect secondary effluent. The required contact times of 30–60 min were also comparable. Utilized ozone doses of 2–4 mg l⁻¹ were required to reduce seeded poliovirus to less than detectable levels in AWT effluent. Naturally-occurring fecal coliform organisms were unaffected at these ozone doses, but were inactivated at higher doses. Because they were more resistant than seeded poliovirus to ozone, fecal coliform organisms show promise as indicators for ozone disinfection.     

Contaminated Land Remediation in the UK with Reference to Risk Assessment: Two Case Studies

The approach to land reclamation in the UK has traditionally relied upon the use of cover and concealment, which can leave a legacy of problems below the ground. Alternatively, the bulk export of materials to licensed landfill has often been used, but this (a) simply transfers a problem, (b) can cause considerable disruption, and (c) is becoming increasingly expensive. Remedial strategies involving the use of barrier systems or off-site removal both have their place in the efficient and economic development of contaminated sites. However, there is now increasing interest in the use of on-site technology which can provide cost savings and by treating, destroying or stabilizing contamination, can serve to minimize future liabilities. The design, costing and application of treatment, as opposed to cover or disposal, depends fundamentally on understanding the problem and evaluating the capabilities and availability of appropriate technologies. With reference to UK case studies, this paper highlights some of the options available and routes taken in order to achieve site-specific, commercially-acceptable, remedial responses.     

The immunochemical detection of stress proteins in activated sludge exposed to toxic chemicals

The heat shock protein, GroEL, was found to be induced in activated sludge cultures exposed to perturbations of chemicals (cadmium, pentachlorophenol, and acetone) or heat stress. In laboratory activated sludge reactors, GroEL was rapidly induced (within minutes) in the presence of 5 mg/l or greater total cadmium. At 5 mg/l cadmium, however, moderate to insignificant changes in activated sludge process performance indicators [effluent suspended solids concentration, chemical oxygen demand (COD) removal, and specific oxygen uptake rate] were observed. As total cadmium concentrations increased above 5 mg/l, there was a significant and consistent increase in effluent volatile suspended solids concentrations from activated sludge sequencing batch reactors relative to unstressed controls. These results indicate that stress proteins may serve as sensitive and rapid indicators of mixed liquor toxicity which can adversely impact treatment process performance, but that GroEL may not be a good candidate protein for this purpose.     

Life Cycle Assessment of urban wastewater reuse with ozonation as tertiary treatment: A focus on toxicity-related impacts

Life Cycle Assessment has been used to compare different scenarios involving wastewater reuse, with special focus on toxicity-related impact categories. The study is based on bench-scale experiments applying ozone and ozone in combination with hydrogen peroxide to a wastewater effluent from a Spanish sewage treatment plant. Two alternative characterisation models have been used to account for toxicity of chemical substances, namely USES-LCA and EDIP97. Four alternative scenarios have been assessed: wastewater discharge plus desalination supply, wastewater reuse without tertiary treatment, wastewater reuse after applying a tertiary treatment consisting on ozonation, and wastewater reuse after applying ozonation in combination with hydrogen peroxide. The results highlight the importance of including wastewater pollutants in LCA of wastewater systems assessing toxicity, since the contribution of wastewater pollutants to the overall toxicity scores in this case study can be above 90%. Key pollutants here are not only heavy metals and other priority pollutants, but also non-regulated pollutants such as pharmaceuticals and personal care products. Wastewater reuse after applying any of the tertiary treatments considered appears as the best choice from an ecotoxicity perspective. As for human toxicity, differences between scenarios are smaller, and taking into account the experimental and modelling uncertainty, the benefits of tertiary treatment are not so clear. From a global warming potential perspective, tertiary treatments involve a potential 85% reduction of greenhouse gas emissions when compared with desalination.     

Life cycle assessment of a coupled solar photocatalytic-biological process for wastewater treatment

A comparative life cycle assessment (LCA) of two solar-driven advanced oxidation processes, namely heterogeneous semiconductor photocatalysis and homogeneous photo-Fenton, both coupled to biological treatment, is carried out in order to identify the environmentally preferable alternative to treat industrial wastewaters containing non-biodegradable priority hazardous substances. The study is based on solar pilot plant tests using alpha-methyl-phenylglycine as a target substance. The LCA study is based on the experimental results obtained, along with data from an industrial-scale plant. The system under study includes production of the plant infrastructure, chemicals, electricity, transport of all these materials to the plant site, management of the spent catalyst by transport and landfilling, as well as treatment of the biodegradable effluent obtained in a conventional municipal wastewater treatment plant, and excess sludge treatment by incineration. Nine environmental impact categories are included in the LCA: global warming, ozone depletion, human toxicity, freshwater aquatic toxicity, photochemical ozone formation, acidification, eutrophication, energy consumption, and land use. The experimental results obtained in the pilot plant show that solar photo-Fenton is able to obtain a biodegradable effluent much faster than solar heterogeneous photocatalysis, implying that the latter would require a much larger solar collector area in an industrial application. The results of the LCA show that, an industrial wastewater treatment plant based on heterogeneous photocatalysis involves a higher environmental impact than the photo-Fenton alternative, which displays impact scores 80-90% lower in most impact categories assessed. These results are mainly due to the larger size of the solar collector field needed by the plant.     

Aspects of water quality and the toxicity of copper to rainbow trout

Studies were made of the effects of additions of a sewage effluent, an amino acid, humic substances, and suspended organic matter on the acute lethal toxicity of water containing copper sulphate to rainbow trout. In all cases the toxicity of a given total concentration of copper was quantitatively reduced. It was concluded that neither the total concentration of copper nor that of “soluble” copper in a water could be used to determine the toxicity to fish which was attributable to copper. It was also concluded that data from toxicity tests with copper in which natural surface waters are used for dilution purposes cannot define the true toxicity of copper or have application to other natural waters except when the concentrations of the toxic chemical species are known.     

Bioassays as a tool for evaluating advanced oxidation processes in water and wastewater treatment

Advanced oxidation processes (AOPs) have been widely used in water and wastewater treatment for the removal of organic and inorganic contaminants as well as to improve biodegradability of industrial wastewater. Unfortunately, the partial oxidation of organic contaminants may result in the formation of intermediates more toxic than parent compounds. In order to avoid this drawback, AOPs are expected to be carefully operated and monitored, and toxicity tests have been used to evaluate whether effluent detoxification takes place. In the present work, the effect of AOPs on the toxicity of aqueous solutions of different classes of contaminants as well as actual aqueous matrices are critically reviewed. The dualism toxicity-biodegradability when AOPs are used as pre-treatment step to improve industrial wastewater biodegradability is also discussed. The main conclusions/remarks include the followings: (i) bioassays are a really useful tool to evaluate the dangerousness of AOPs as well as to set up the proper operative conditions, (ii) target organisms for bioassays should be chosen according to the final use of the treated water matrix, (iii) acute toxicity tests may be not suitable to evaluate toxicity in the presence of low/realistic concentrations of target contaminants, so studies on chronic effects should be further developed, (iv) some toxicity tests may be not useful to evaluate biodegradability potential, in this case more suitable tests should be applied (e.g., activated sludge bioassays, respirometry).     

Treatment of olive oil mill wastewater by combined process electro-Fenton reaction and anaerobic digestion

In this work, we investigated an integrated technology for the treatment of the recalcitrant contaminants of olive mill wastewaters (OMW), allowing water recovery and reuse for agricultural purposes. The method involves an electrochemical pre-treatment step of the wastewater using the electro-Fenton reaction followed by an anaerobic bio-treatment. The electro-Fenton process removed 65.8% of the total polyphenolic compounds and subsequently decreased the OMW toxicity from 100% to 66.9%, which resulted in improving the performance of the anaerobic digestion. A continuous lab-scale methanogenic reactor was operated at a loading rate of 10 g chemical oxygen demand (COD)l(-1) d(-1) without any apparent toxicity. Furthermore, in the combined process, a high overall reduction in COD, suspended solids, polyphenols and lipid content was achieved by the two successive stages. This result opens promising perspectives since its conception as a fast and cheap pre-treatment prior to conventional anaerobic post-treatment. The use of electro-coagulation as post-treatment technology completely detoxified the anaerobic effluent and removed its toxic compounds.     

Oxygen uptake studies on various sludges adapted to a waste containing chloro-, nitro- and amino-substituted xenobiotics

Although containing very low concentrations of organics, triaminotrinitrobenzene (TATB) effluent still appeared toxic in shake-flask experiments. Few toxicity effects showed in model activated-sludge plants, provided that these contained suitably adapted organisms, and were run on phenolic waste or phenol as a basic carboniferous load. Oxygen uptake studies indicated that the metabolic processes within the sludge population appeared unusual, and that degradation of TATB effluent required a sludge which was specially adapted.     

The fate of wastewater-derived NDMA precursors in the aquatic environment

To assess the stability of precursors of the chloramine disinfection byproduct N-nitrosodimethylamine (NDMA) under conditions expected in effluent-dominated surface waters, effluent samples from four municipal wastewater treatment plants were subjected to chlorination and chloramination followed by incubation in the presence of inocula derived from activated sludge. Samples subjected to free chlorine disinfection showed lower initial concentrations of NDMA precursors than those that were not chlorinated or were disinfected with pre-formed chloramines. For chloraminated and control (unchlorinated) treatments, the concentration of NDMA precursors decreased by an average of 24% over the 30-day incubation in samples from three of the four facilities. At the fourth facility, where samples were collected on three different days, NDMA precursor concentrations decreased by approximately 80% in one sample and decreased by less than 20% in the other two samples. In contrast to the low reactivity of the NDMA precursors, NDMA disappeared within 30 days under the conditions employed in these experiments. These results and measurements made in an effluent-dominated river suggest that although NDMA may be removed after wastewater effluent is discharged, wastewater-derived NDMA precursors could persist long enough to form significant concentrations of NDMA in drinking water treatment plants that use water originating from sources that are subjected to wastewater effluent discharges.     

Combined biological and ozone treatment of log yard run-off

Batch biological treatment of log yard run-off reduced biochemical oxygen demand (BOD), chemical oxygen demand (COD) and tannin and lignin (TL) concentration by 99%, 80%, and 90%, respectively. Acute (Microtox) toxicity was decreased over treatment, from an initial EC50 of 1.83% to a value of 50.4% after 48 h of treatment. Kinetics of biodegradation were determined using respirometry and fitted using the Monod and Tessier model. For the Monod model the maximum substrate uptake rate, and Ks values determined were 0.0038 mg BOD/mgVSS min, and 1.4 mg/L, respectively. The efficacy of ozone as a pre- and post- biological treatment stage was also assessed. During ozone pretreatment, TL concentration and acute toxicity were rapidly reduced by 70% and 71%, respectively. Pre-ozonation reduced BOD and COD concentration by < 10%, however a larger fraction of residual COD was non biodegradable after ozonation. Biologically treated effluent was subjected to ozonation to determine whether further improvements in effluent quality could be achieved. A reduction in COD and TL concentration was observed during ozonation, however no further improvement in toxicity was observed. Ozonation increased BOD by 38%, due to conversion of COD to BOD.     

Algal-bacterial processes for the treatment of hazardous contaminants: a review

Microalgae enhance the removal of nutrients, organic contaminants, heavy metals, and pathogens from domestic wastewater and furnish an interesting raw material for the production of high-value chemicals (algae metabolites) or biogas. Photosynthetic oxygen production also reduces the need for external aeration, which is especially advantageous for the treatment of hazardous pollutants that must be biodegraded aerobically but might volatilize during mechanical aeration. Recent studies have therefore shown that when proper methods for algal selection and cultivation are used, it is possible to use microalgae to produce the O(2) required by acclimatized bacteria to biodegrade hazardous pollutants such as polycyclic aromatic hydrocarbons, phenolics, and organic solvents. Well-mixed photobioreactors with algal biomass recirculation are recommended to protect the microalgae from effluent toxicity and optimize light utilization efficiency. The optimum biomass concentration to maintain in the system depends mainly on the light intensity and the reactor configuration: At low light intensity, the biomass concentration should be optimized to avoid mutual shading and dark respiration whereas at high light intensity, a high biomass concentration can be useful to protect microalgae from light inhibition and optimize the light/dark cycle frequency. Photobioreactors can be designed as open (stabilization ponds or high rate algal ponds) or enclosed (tubular, flat plate) systems. The latter are generally costly to construct and operate but more efficient than open systems. The best configuration to select will depend on factors such as process safety, land cost, and biomass use. Biomass harvest remains a limitation but recent progresses have been made in the selection of flocculating strains, the application of bioflocculants, or the use of immobilized biomass systems.     

Physical methods of liquid effluent treatment — separation processes

Most effluent treatment processes require at least one physical separation stage. Sometimes gravity sedimentation is the preferred route, but there are often good reasons for the selection of a more intensive, electrically-based technique, writes Alison Bettley. There are many such existing processes to choose from. With increasingly rigorous pollution control regulations, the use of higher performance and more intensive separation processes will grow. Moreover, the increasing emphasis on materials conservation and recovery, including water re-use, will reinforce this trend. There is therefore considerable opportunity to increase the penetration of electrical techniques for physical separation processes in the effluent treatment market.