The Application of Semiconductor Photocatalysis for the Removal of Cyanotoxins from Water and Design Concepts for Solar Photocatalytic Reactors for Large Scale Water Treatment

There has been a significant increase in the occurrence of cyanobacterial blooms in freshwaters over the past few decades due to escalating nutrient levels. These cyanobacteria release a range of toxins, for example microcystins which are chemically very stable. Many cyanotoxins are consequently very difficult to remove from water using existing treatment technologies. Semiconductor photocatalysis, however, has proven to be a very effective process for the removal of these compounds from water. In this chapter we consider the application of this highly versatile and exciting technology for the decomposition of cyanotoxins. Furthermore design concepts for solar photocatalytic reactors that could be utilized for the removal of these toxins are also considered

Quantifying mircoorganism/organic matter interactions in saturated porous media.

Proteins and humic acids are common constituents of waste water. Latex colloids (colloids) acted as surrogates for microorganisms in multiple pulse dynamic column experiments (MPEs) that permitted colloid mobility to be quantified before and after the injection of either BSA (a protein), or Suwannee River humic acid (SRHA).
At low OM coverage colloid breakthrough curves demonstrated both BSA and SRHA reduced colloid deposition rates, but did not affect colloid irreversible deposition mechanisms. By contrast, high levels of SRHA surface coverage not only further reduced the matrix’s ability to attenuate colloids, but also resulted in reversible adsorption of a significant fraction of colloids deposited. Modelling of colloid responses using random sequential adsorption modelling suggested that 1 microgram of SRHA had the same effect as the deposition of 5.90±0.14 x109 colloids; the model suggested that adsorption of the same mass of BSA was equivalent to the deposition of between 7.1x108 and 2.3x109 colloids.
Colloid responses in MPEs where BSA coverage of colloid deposition sites approached saturation demonstrated the sand matrix remained capable of adsorbing colloids. However, in contrast to responses observed in MPEs at low surface coverage, continued colloid injection showed that the sand’s attenuation capacity increased with time, i.e. colloid concentrations declined as more were deposited (filter ripening).
Importance: Study results highlight the contrasting responses that may arise due to the interactions between colloids and OM in porous media. Results not only underscore that colloids can interact differently with various forms of deposited OM, but also that a single type of OM may generate dramatically different responses depending on the degree of surface coverage. The MPE method provides a means of quantifying the influence of OM on microorganism mobility in porous media such as filter beds, which may be used for either drinking water treatment or waste water treatment. In the wider environment study findings have potential to allow more confident predictions of the mobility of sewage derived pathogens discharging to groundwater.

Removal of ortho-phosphate from aqueous solution by adsorption onto dolomite

An experimental study on the adsorption of phosphate onto cost effective fine dolomite powder is presented. The effect of solution pH, solution ionic strength and adsorption isotherm were examined. The adsorption of phosphate was pH dependent and phosphate adsorption favoured acidic conditions. The adsorption was significantly influenced by solution ionic strength indicating outer-sphere complexation reactions. The experimental data further indicated that the removal of phosphate increased with increase in the ionic strength of solution. The experimental data were modelled with different isotherms: Langmuir, Freundlich and Redlich–Peterson isotherms. It was found that the Redlich–Peterson isotherm depicted the equilibrium data most accurately. The overall kinetic data fitted very well the pseudo-first-order rate model.

Synthesis of caffeic acid and p-hydroxybenzoic acid molecularly imprinted polymers and their application for the selective extraction of polyphenols from olive mill waste waters

Using caffeic acid and p-hydroxybenzoic acid as templates, two molecularly imprinted polymers (MIPs) were prepared that were used for isolation of polyphenols from olive mill waste water samples (OMWWs) without previous pre-treatment. For the preparation of the caffeic acid MIPs 4-vinylpyridine, allylurea, allylaniline and methacrylic acid were tested as functional monomers, ethylene glycol dimethylacrylate (EDMA), pentaerythritol trimethylacrylate (PETRA) and divinylbenzene 80 (DVB80) as cross-linkers and tetrahydrofuran as porogen. For p-hydroxybenzoic acid 4-vinylpyridine, allylurea and allylaniline were tested as functional monomers, EDMA and PETRA as cross-linkers and acetonitrile as porogen. The performance of the synthesized polymers was evaluated against seven structurally related compounds by means of polymer-based HPLC. The two polymers that presented the most interesting properties were further evaluated by batch rebinding and from the derived isotherms their capacity and binding strength were determined. Using solid-phase extraction (SPE), their ability to recognize and bind the template molecule from an aqueous solution as well as the pH dependence of the binding strength were explored. After establishing the best SPE protocol, an aqueous model mixture of compounds and a raw OMWWs sample were loaded on the two best polymers. The result of the consecutive use of the two polymers on the same sample was explored. It was concluded that acidic conditions favour the recognition abilities of both polymers and that they can be used for a quick and efficient isolation of the polyphenol fraction directly from raw OMWW.

COD removal from textile industry effluent: pilot plant studies

This work involved the treatment of industrial waste water from a nylon carpet printing plant. As dyeing of nylon is particularly difficult, acid dyes, fixing agents, thickeners, finishing agents, are required for successful colouration and cause major problems with the plant's effluent disposal in terms of chemical oxygen demand (COD). Granular activated carbon (GAC) Filtrasorb 400 was used to treat a simulated process plant effluent containing all the pollutants. Equilibrium isotherm experiments were established and experimental data obtained showed good empirical correlation with Langmuir isotherm theory. Column experimental data, in terms of COD were correlated using the bed depth service time (BDST) model. Solid phase loading in the columns were found to approach that in equilibrium studies indicating an efficient use of adsorbent. The results from the BDST model were then used to design a pilot adsorption rig at the plant. The performance of the pilot plant column were accurately predicted by scale-up from the bench scale columns. (C) 2001 Elsevier Science BN. All rights reserved.

Effectiveness of different footbath solutions in the treatment of digital dermatitis in dairy cows

Three experiments were conducted to test the effectiveness of different footbath solutions and regimens in the treatment of digital dermatitis (DD) in dairy cows. During the study, groups of cows walked through allocated footbath solutions after milking on 4 consecutive occasions. All cows were scored weekly for DD lesion stage on the hind feet during milking. A “transition grade” was assigned on the basis of whether the DD lesions improved (1) or deteriorated or did not improve (0) from week to week. This grade per cow was averaged for all cows in the group. In experiment 1, 118 cows were allocated to 1 of 3 footbath treatments for 5 wk: (1) 5% CuSO4 each week, (2) 2% ClO- each week, or (3) no footbath (control). The mean transition grade, and proportion of cows without DD lesions at the end of the trial were significantly higher for treatment 1 above (0.36, 0.13, and 0.11, respectively; standard error of the difference, SED=0.057). In experiment 2, 117 cows were allocated to 1 of 4 footbath treatment regimens for 8 wk: (1) 5% CuSO4 each week, (2) 2% CuSO4 each week, (3) 5% CuSO4 each fortnight, or (4) 2% CuSO4 each fortnight. For welfare reasons, cows allocated to the weekly and fortnightly footbath regimens had an average prevalence of >60% and =25% active DD at the start of the trial, respectively. Significantly more cows had no DD lesions (0.53 vs. 0.36, respectively; SED=0.049), and the mean transition grade of DD lesions was higher in the 5% compared with the 2% weekly CuSO4 treatment (0.52 vs. 0.38, respectively; SED=0.066). Similarly, significantly more cows had no DD lesions in the 5% compared with the 2% fortnightly CuSO4 treatments (0.64 vs. 0.47, respectively; SED=0.049). In experiment 3, 95 cows were allocated to 1 of 3 footbath treatments: (1) each week alternating 5% CuSO4 with 10% salt water, (2) each week alternating 5% CuSO4 with water, or (3) 5% CuSO4 each fortnight (control). After 10 wk, more cows had no DD in the salt water treatment than in the control treatment (0.35 vs. 0.26, respectively; SED=0.038), but levels of active lesions were higher for this treatment than in the other 2 treatments (0.17, 0.00, and 0.13, respectively; SED=0.029). Treatment did not affect mean transition grade of DD lesions. In conclusion, CuSO4 was the only footbath solution that was consistently effective for treatment of DD. In cases when DD prevalence was high, a footbath each week using 5% CuSO4 was the most effective treatment.

Alternative method for producing organic fertiliser from anaerobic digestion liquor and limestone powder:High Shear wet granulation

Generally, the solid and liquid fractions (digestate) from Anaerobic Digestion (AD) energy production are considered as waste. This has a negative impact on the sustainability of AD processes because of the financial outlay required to treat digestate before being discharged into municipal water treatment plants or natural water bodies. The main aim of this research was to investigate feasibility of producing an organic fertiliser using anaerobic digestate and limestone powders as the raw materials employing a high shear granulation process. Two-level factorial experimental design was used to determine the influence of granulation process variables on, the strength, resistance to attrition and yield of the granules. It was concluded from the study that it is technically feasible to produce organic fertiliser granules of acceptable strength and product yield. Increasing the liquid-to-solid ratio during granulation leads to increased granule strength and better product yield. Although the strength of the granules produced was lower than typical strength of commercial synthetic fertiliser granules (about 5 to 7. MPa), this could be improved by mixing the digestate with a polymeric binder or coating the particles post granulation. © 2012 Elsevier B.V.

Photocatalytic reactors for environmental remediation: A review

Research in the field of photocatalytic reactors in the past three decades has been an area of extensive and diverse activity with an extensive range of suspended and fixed film photocatalyst configurations being reported. The key considerations for photocatalytic reactors, however, remain the same; effective mass transfer of pollutants to the photocatalyst surface and effective deployments and illumination of the photocatalyst. Photocatalytic reactors have the potential versatility to be applied to the remediation of a range of water and gaseous effluents. Furthermore they have also been applied to the treatment of potable waters. The scale-up of photocatalytic reactors for waste and potable water treatment plants has also been demonstrated. Systems for the reduction of carbon dioxide to fuel products have also been reported. This paper considers the main photocatalytic reactor configurations that have been reported to date. 

Remediation of oily wastewater from an interceptor tank using a novel photocatalytic drum reactor

A novel photocatalytic reactor has been developed to remediate oily wastewaters. In the first instance degradation rates of model organic compounds, methylene blue (MB) and 4-c hlorophenol (4-CP) were determined. The experimental set-up investigated a 1:10 w/v catalyst to organic solution volume, 30 g catalyst, 300 mls MB (10 μM) or 4-CP (100 μM). The catalyst investigated was a pellet catalyst to improve separation of the remediated volume from the catalyst following treatment. MB concentration decreased by 93% after 15 mins irradiation whilst 4-CP concentration decreased by 94% following 90 mins irradiation. Oily waste water (OWW) from an interceptor tank typically containing diesel oils was obtained from Sureclean, an environmental clean-up company. The OWW was treated using the same conditions as MB and 4-CP, the model organic compounds. Levels of total organic carbon (TOC) and total petroleum hydrocarbon (TPH) were used to monitor the efficacy of the photocatalytic reactor. TOC reduced by 45% following two 90 mins treatment cycles. TPH reduced by 45% following 90 mins irradiation and by a further 25% during a second stage of treatment. This reactor can be used as a polishing technique assembled within a wastewater treatment plant. Allowing for more than one pass through the reactor improves its efficiency. 

Novel photocatalytic reactor development for removal of hydrocarbons from water

Hydrocarbons contamination of the marine environment generated by the offshore oil and gas industry is generated from a number of sources including oil contaminated drill cuttings and produced waters. The removal of hydrocarbons from both these sources is one of the most significant challenges facing this sector as it moves towards zero emissions. The application of a number of techniques which have been used to successfully destroy hydrocarbons in produced water and waste water effluents has previously been reported. This paper reports the application of semiconductor photocatalysis as a final polishing step for the removal of hydrocarbons from two waste effluent sources. Two reactor concepts were considered: a simple flat plate immobilised film unit, and a new rotating drum photocatalytic reactor. Both units proved to be effective in removing residual hydrocarbons from the effluent with the drum reactor reducing the hydrocarbon content by 90% under 10 minutes.