José F. Casanueva

Comparative effect of simulated solar light, UV, UV/H2O2 and photo-Fenton treatment (UV-Vis/H2O2/Fe2+,3+) in the Escherichia coli inactivation in artificial seawater.

Innovative disinfection technologies are being studied for seawater, seeking a viable alternative to chlorination. This study proposes the use of H2O2/UV254 and photo-Fenton as disinfection treatment in seawater. The irradiations were carried out using a sunlight simulator (Suntest) and a cylindrical UV reactor. The efficiency of the treatment was compared for Milli-Q water, Leman Lake water and artificial seawater. The presence of bicarbonates and organic matter was investigated in order to evaluate possible effects on the photo-Fenton disinfection treatment. The photo-Fenton treatment, employing 1 mg L(-1) Fe(2+) and 10 mg L(-1) of H2O2, led to the fastest bacterial inactivation kinetics. Using H2O2/UV254 high disinfection rates were obtained similar to those obtained with photo-Fenton under UV254 light. In Milli-Q water, the rate of inactivation for Escherichia coli was higher than in Leman Lake water and seawater due to the lack of inorganic ions affecting negatively bacteria inactivation. The presence of bicarbonate showed scavenging of the OH(•) radicals generated in the treatment of photo-Fenton and H2O2/UV254. Despite the negative effect of inorganic ions, especially HCO3(-), the disinfection treatments with AOPs in lake water and seawater improved significantly the disinfection compared to light alone (simulated sunlight and UV254). In the treatment of photo-Fenton with simulated sunlight, dissolved organic matter had a beneficial effect by increasing the rate of inactivation. This is associated with the formation of Fe(3+)-organo photosensitive complexes leading to the formation of ROS able to inactivate bacteria. This effect was not observed in the photo-Fenton with UV254. Growth of E. coli surviving in seawater was observed 24 and 48 h after treatment with UV light. However, growth of surviving bacteria was not detected after photo-Fenton with UV254 and H2O2/UV254 treatments. This study suggests H2O2/UV254 and photo-Fenton treatments for the disinfection of seawater, in spite its high concentration of salts.

Biomarker responses in Solea senegalensis exposed to sodium hypochlorite used as antifouling

The time-course stress responses (0, 1, 2, and 7 d) was assessed in plasmatic, branchial and renal parameters of juveniles Solea senegalensis exposed to different concentrations of the antifouling sodium hypochlorite (0.1, 0.2, and 0.5mgL(-1)). These stress responses were only assessed for the total length of exposure (7d) at the lowest NaClO concentration due to the high toxicity of this chemical. In addition, the xenobiotic metabolism responses were evaluated by means of enzymatic activities of ethoxyresorufin O-deethylase (EROD), glutathione S-transferase (GST), glutathione reductase (GR), glutathione peroxidase (GPX), catalase (CAT), and carboxylesterase (CbE) in liver; as well as GST, GPX, CAT and acetylcholinesterase (AChE) in gill. Oxidative stress damage due to sodium hypochlorite exposure was measured by lipid peroxidation levels in liver and gill. Concentrations of 0.2 and 0.5mgL(-1) produced lethal effects after 1d and 2h of exposure, respectively. After 1d of exposure to sublethal concentration of sodium hypochlorite (0.1mgL(-1)) osmoregulatory (osmolality and chloride) and stress (cortisol, glucose and lactate) plasmatic parameters were enhanced to respect at control fish. However after 3 or 7d these parameters returned to control values. No effects were observed on plasma protein and triglyceride levels or on gill and kidney Na(+)/K(+)-ATPase activities. Diverse gill pathologies such as hypertrophy, lamellar fusion and an increase in goblet cell number and size were observed after 7d of exposure. Most biochemical parameters related to xenobiotic metabolism and oxidative stress were also significantly affected which suggests that seawater affected by sodium hypochlorite discharges from power plants, is able to alter the fish xenobiotic metabolism and generate oxidative stress.

Degradation models and ecotoxicity in marine waters of two antifouling compounds: Sodium hypochlorite and an alkylamine surfactant

Industrial wastes have a substantial impact on coastal environments. Therefore, to evaluate the impact of cooling water discharges from coastal power plants, we studied the kinetics of the degradative processes and the ecotoxicity of two antifouling products: (1) a classic antifouling product; sodium hypochlorite (NaClO) and (2) an alternative one; aliphatic amines (commercial under the registered trade mark Mexel432). To assess the persistence of both compounds the decay of sodium hypochlorite and the primary biodegradation rate of Mexel432 were determined in natural seawater at 20 degrees C. The results indicated a more rapid decay of NaClO than Mexel432. The degradation behavior of both chemicals was described following a logistic model, which permitted calculating kinetic parameters such as t(50) or t(90). The t(50) was 1h and 2d for NaClO and Mexel432, respectively. To evaluate the potential risks of the aforementioned treatments to marine organisms, the acute toxicity of both antifouling products was studied on the microalgae Isochrysis galbana and Dunaliella salina, and on the invertebrate Brachionus plicatilis, using growth inhibition and death tests as toxic response, respectively. For I. galbana, the 96-h EC(50) values were 2.91+/-0.15mg/L of NaClO and 4.55+/-0.11mg/L of Mexel432. D. salina showed values of 96-h EC(50) of 1.73+/-0.16mg/L of NaClO and 7.21+/-0.1mg/L of Mexel432. Brachionus plicatilis showed a 24-h LC(50) of 1.23+/-0.1mg/L of NaClO and 3.62+/-0.37mg/L of Mexel432. Acute toxicity was highly dependent on the chemical and species tested. NaClO presented more toxic effects than Mexel432, also B. plicatilis was the most sensitive species in both cases. The lowest NOECs obtained, 0.25mg/L for NaClO and 2.12mg/L for Mexel432, were similar to the theoretical residual concentrations of these biocides in cooling water discharges. Therefore, these discharges can cause undesirable negative effects upon the aquatic organisms present.

Efficacy of different antifouling treatments for seawater cooling systems

In an industrial seawater cooling system, the effects of three different antifouling treatments, viz. sodium hypochlorite (NaClO), aliphatic amines (Mexel®432) and UV radiation, on the characteristics of the fouling formed were evaluated. For this study a portable pilot plant, as a side-stream monitoring system and seawater cooling system, was employed. The pilot plant simulated a power plant steam condenser, having four titanium tubes under different treatment patterns, where fouling progression could be monitored. The nature of the fouling obtained was chiefly inorganic, showing a clear dependence on the antifouling treatment employed. After 72 days the tubes under treatment showed a reduction in the heat transfer resistance (R) of around 70% for NaClO, 48% for aliphatic amines and 55% for UV, with respect to the untreated tube. The use of a logistic model was very useful for predicting the fouling progression and the maximum asymptotic value of the increment in the heat transfer resistance (ΔR max). The apparent thermal conductivity (λ) of the fouling layer showed a direct relationship with the percentage of organic matter in the collected fouling. The characteristics and mode of action of the different treatments used led to fouling with diverse physicochemical properties.

Sublethal responses of the common mussel (Mytilus galloprovincialis) exposed to sodium hypochlorite and Mexel®432 used as antifoulants.

The sublethal effects of two antifoulants currently used in power plant cooling systems were assessed in the common mussel Mytilus galloprovincialis. The concentrations of sodium hypochlorite (NaClO) and an alkyl amine surfactant (Mexel432) assayed, were within the range of those currently discharged by power plants into receiving waters. Enzymatic activities and oxidative stress responses were measured in digestive gland and gill of mussels after 1, 3, 7 and 14 days of exposure, as well as histopathology in gill tissue. Both antifoulants caused a pathological response in gills and the activities of the enzymes glutathione S-transferase, catalase, acetylcholinesterase and the lipid peroxidation levels were also affected. Exposure to NaClO caused a greater toxicological response than Mexel432. In both treatments, gills appeared to be the most affected tissue, although Mexel432 also significantly affected digestive gland parameters.

Sublethal effects of the organic antifoulant Mexel® 432 on osmoregulation and xenobiotic detoxification in the flatfish Solea senegalensis

Mexel(R)432 is an anionic surfactant used as biocide in the cooling water system of power plants for biofouling reduction. Refrigeration waters from power plants do not usually follow, prior to their discharge to sea, any treatment aimed to eliminate biocides and this can have negative consequences on the aquatic fauna nearby. The effects of different concentrations of the antifoulant Mexel(R)432 (0.5, 1 and 2mgL(-1)) on osmoregulation (osmolality and Na(+)/K(+)-ATPase activity) and stress parameters (cortisol, glucose, and lactate) were assessed in juveniles of the flatfish Solea senegalensis. Gill histopathology and alterations due to oxidative stress (increased lipid peroxidation, LPO, levels) at branchial and hepatic levels were also considered. Other parameters tested were the antioxidant enzymes (catalase, CAT; glutathione peroxidase, GPX; and glutathione reductase, GR), xenobiotic metabolism defenses involved in detoxification (carboxylesterase, CbE; 7-ethoxyresorufin O-deethylase, EROD; and glutathione S-transferase, GST) and the neurotransmitter acetylcholinesterase (AChE) activity. Significant variations in osmoregulatory parameters, histological lesions and decreased branchial Na(+)/K(+)-ATPase activity were observed in exposed fish. Other gill biomarkers presented little or no significant variations in relation to controls. In contrast, hepatic parameters, such as CAT activity, were inhibited while EROD activity was initially elevated but after longer exposures it recovered basal values. These results suggested that under our experimental protocol exists toxic associated to Mexel(R)432 exposures.