Disinfection By-Products Formation from Chlor(am)ination of Algal Organic Matter of Chlorella sorokiniana.

Eutrophication in water reservoirs releases algal organic matter (AOM), which is an important precursor of disinfection by-products (DBPs) formed during water treatment. Chlorella sorokiniana is a microalgae which flourishes under conditions of high light intensity and temperature, thus its prevalence in algal blooms is expected to increase with climate change. However, Chlorella sorokiniana AOM has not been previously investigated as a DBP precursor. In this context, this study evaluated the effect of AOM concentration, humic acid (HA), and pH on DBP formation from chlor(am)ination of AOM Chlorella sorokiniana. DBP yields determined by linear regression for trichloromethane (TCM) and chloral hydrate (CH) were 57.9 and 46.0 µg·mg DOC-1 in chlorination, while the TCM, CH, dichloroacetonitrile (DCAN), 1,1,1-trichloropropanone (1,1,1-TCP), and chloropicrin (CPN) concentrations were 33.6, 29.8, 16.7, 2.1, and 1.2 µg·mg DOC-1 in chloramination. Chloramination reduced the formation of TCM and CH but increased CPN, DCAN, and 1,1,1-TCP yields. AOM Chlorella sorokiniana showed a higher DBP formation than 9 of 11 algae species previously investigated in the literature. At basic pH, the concentration of TCM increased while the concentration of other DBP classes decreased. Bromide was effectively incorporated into the AOM structure and high values of bromine incorporation factor were found for THM (1.81-1.89) and HAN (1.32) at 1.5 mg Br·L-1. Empirical models predicted successfully the formation of THM and HAN (R2 > 0.86). The bromide concentration had more impact in the model on the DBP formation than AOM and HA. These results provide the first insights into the DBP formation from AOM chlor(am)ination of Chlorella sorokiniana.

Membrane aerated biofilm reactor in recirculating aquaculture system for effluent treatment.

The implementation of fish farming has been increasing worldwide over the last decades, as well the search for alternative production systems and the treatment of their generated effluent. Recirculating Aquaculture System (RAS) is a compact solution for future intensive fish farming. However, few configurations of treatment technologies were tested in RAS, such as systems with a Membrane Aerated Biofilm Reactor (MABR). In this scene, this study aimed to evaluate the RAS effluent treatment efficiency device for intensive Nile tilapia (Oreochromis niloticus) production, the fish species most cultivated worldwide. The novel RAS configuration was composed of a cultivation tank (CT), a Column Settler, and a MABR. The RAS performance was evaluated by pH, temperature, turbidity, dissolved oxygen (DO), total nitrogen (TN), ammonia, nitrite, nitrate, total solids (TS), and chemical oxygen demand (COD). The obtained results in average values for temperature, pH, and DO inside the CT were 25.22 ± 1.88°C, 7.61 ± 0.33, and 3.80 ± 1.30 mg L-1, respectively, as ideal for tilapias survival. Average removal efficiencies found in the RAS for turbidity, COD, TN, nitrite, nitrate, ammonia, and TS were 50.0, 40.5, 11.7, 40.2, 13.1, 35.0, and 11.4%, respectively. Overall, we observed removals for all parameters studied, with good results, particularly, for COD, turbidity, nitrite, and ammonia. The evaluated system proved an effective alternative for water reuse in RAS capable of maintaining water quality characteristics within the recommended values for fish farming.

Screening of new adsorbents to remove algal organic matter from aqueous solutions: kinetic analyses and reduction of disinfection by-products formation.

The algal organic matter (AOM) is a problem in water treatment. Although the adsorption process is extensively applied to drinking water treatment, little information is known about the potential of new adsorbents to remove AOM. Herein, this work evaluated the removal of AOM and its main compounds (dissolved organic carbon (DOC), carbohydrate, and protein) by new adsorbents-mesoporous silica (SBA-16), graphene oxide material from citric acid (CA), and sugar (SU), and a composite of CA immobilized on sand (GSC). In general, the removal efficiencies followed the order of SBA-16 > CA > SU or GSC for DOC, carbohydrate, and protein. At environmental condition (5 mg DOC·L-1 and pH 8), high removals were reported for SBA-16 (88.8% DOC, 80.0% carbohydrate, and 99.6% protein) and CA (70.0% DOC, 66.7% carbohydrate, and 89.7% protein), while moderate removals were found for SU (60.5% DOC, 47.9% carbohydrate, and 66.5% protein) and GSC (67.4% DOC, 60.8% carbohydrate, and 57.4% protein). Based on these results, further analyses were done with SBA-16 and CA. Both adsorbents' efficiencies decayed with the pH increment of the test water. Disinfection by-products reductions found using SBA-16 - trihalomethanes (58.2 to 94.7%) and chloral hydrate (48.7 to 78.8%) - were higher than the ones using CA-trihalomethanes (45.2 to 82.4%) and chloral hydrate (40.1 to 70.8%). This study showed the potential of applying these adsorbents for AOM removal, and further investigations are suggested to increase the adsorption capacity of these adsorbents.

Acute toxicity of disinfection by-products from chlorination of algal organic matter to the cladocerans Ceriodaphnia silvestrii and Daphnia similis: influence of bromide and quenching agent.

Algal organic matter (AOM) in water reservoirs is a worldwide concern for drinking water treatment; once it is one of the main precursors for disinfection by-products formation (DBPs). In this context, this study investigated the ecotoxicity of DBPs from chlorination of AOM to Ceriodaphnia silvestrii and Daphnia similis (Crustacea, Cladocera). The bioassays evaluated three scenarios, including the AOM extracted from Chlorella sorokiniana, the quenching condition used in the tests, and the DBPs formed after the chlorination of the two test waters with AOM (with and without bromide presence). The results showed that AOM has no toxic effects for the tested species under typical environmental concentration (5 mg∙L-1). However, since AOM is a potential precursor of DBPs, the toxicity of two test waters (TW-1 and TW-2) after the chlorination process (25 mg Cl2·L-1, for 7 days, at 20 °C) was tested. The sample with higher toxicity to the tested species was TW-1, in which chloroform and chloral hydrate were quantified (615 and 267 µg∙L-1, respectively). However, TW-2 showed lower concentration of chloroform and chloral hydrate (260 and 157 µg∙L-1, respectively), although bromodichloromethane, dibromochloromethane, and bromoform were also detected (464, 366, and 141 µg∙L-1, respectively). Although free chlorine is highly toxic to the tested species, the quenching conditions also affected the organisms' survival due to the use of ascorbic acid and the presence of reaction intermediates. Nonetheless, both species were more affected by TW-1 and TW-2 than the quenching condition. These results endorse the importance of removing the AOM before the disinfection process to avoid the formation of DBPs. In addition, ecotoxicological analyses could provide a more comprehensive assessment of water quality, especially considering the challenges of quantifying DBPs and other emerging contaminants.

Detection and removal of Giardia spp. cysts and Cryptosporidium spp. oocysts by anaerobic reactors in Brazil.

The discharge of raw wastewater into the environment can be a contamination source of Giardia spp. cysts and Cryptosporidium spp. oocysts. The UASB (Upflow Anaerobic Sludge Blanket) reactor is the most popular technology applied for wastewater treatment in Brazil, nevertheless there is little information concerning its capacity for (oo)cyst removal. In this context, this study investigated the occurrence and removal of Giardia spp. cysts and Cryptosporidium spp. oocysts by three different UASB reactors (i.e. Reactor A, B, and C) treating different wastewater types. In the wastewater influent, the concentration varied from 493.3 to 14,000 cysts·L-1 for Giardia spp. and from 'not detected' to 53.3 oocysts·L-1 for Cryptosporidium spp.. The (oo)cyst concentration increased after the anaerobic treatment in Reactors A and B, while Giardia spp. log-removal of 0.5 ± 0.2 was found in Reactor C. The increment in (oo)cyst concentration may happened due to the inefficacy for (oo)cyst removal by the specific UASB reactor and/or due to the reduction of matrix interference for reactor effluent samples in the detection method. The results suggest that hydraulic retention time (HRT) may be the key parameter for Giardia spp. removal by the UASB reactor. Furthermore, no parameter analysed (physical-chemical and indicator microorganisms) showed a common correlation with the (oo)cyst concentration in the three UASB reactors. Considering that official data of cryptosporidiosis and giardiasis cases are rarely reported in Brazil, monitoring Giardia spp. cysts and Cryptosporidium spp. oocysts in wastewater could be an alternative to estimate the occurrence of diseases in the served population.

Removal of protozoan (oo)cysts and bacteria during microalgae harvesting: Outcomes from a lab-scale experiment.

The efficiency of microalgae harvesting on the removal of Giardia spp. cysts, Cryptosporidium spp. oocysts, total coliforms, Escherichia coli, Enterococcus spp. and Clostridium spp. was assessed in lab-scale experiments (Jartest and Flotatest) using effluent from a flat panel photobioreactor used for Chlorella sorokiniana cultivation. Three harvesting methods were evaluated: (1) flocculation induced by pH modulation followed by sedimentation (pH-SED), (2) flocculation induced by pH modulation followed by dissolved air flotation (pH-DAF), and (3) coagulation using an organic coagulant (Tanfloc SG) followed by dissolved air flotation (Coag-DAF). The results indicated that the three harvesting methods were efficient in removing protozoan (oo)cysts and bacteria, achieving percentages of removal higher than 97% for all the analyzed pathogens. Among the three methods, pH-SED showed the best removal performance: 99.60% (2.5 log) for Giardia spp. cysts, 100% (>6.3 log) for total coliforms, 100% (>4.6 log) for Escherichia coli, 100% (>5.8 log) for Enterococcus spp. and 99.96% (3.6 log) for Clostridium spp. Clostridium spp. seemed to be more tolerant to the harvesting methods than the other groups of bacteria analyzed in the study, and its presence was positively correlated to the presence of Giardia spp. cysts.

Implications of COD analysis use in the peracetic acid-based wastewater treatment.

Peracetic acid (PAA) stands out as a safe and environmental-friendly oxidant and disinfectant which has been effectively used in wastewater treatment. Chemical oxygen demand (COD) is a very popular analysis in wastewater treatment; however, the interference of residual PAA on the COD measurement is still unknown. In this context, this study investigated the implications of applying the COD analysis in PAA-based treatment. Each 1 mg·L-1 of PAA increased the COD concentration around 13.5 mg O2·L-1. Residual PAA and hydrogen peroxide (H2O2) were efficiently neutralized by sodium metabisulfite (SMBS) at the optimal SMBS/PAA ratio of 10.2:1 in a wide pH range (5 to 9). The effect of PAA addition on the COD concentration was evaluated in different water matrices (potassium hydrogen phthalate and wastewater solutions). The COD results with the SMBS addition at optimal SMBS/PAA ratio were lower than the ones without it. It may happen due to the neutralization of residual H2O2/PAA and the complexity of the water matrices which can interfere in the COD results. This study discussed the impact of the residual H2O2/PAA neutralization before the COD analysis, and this investigation can be used as a practical guideline for the correct COD measurement in PAA-based treatment.

Optimization of microalgae harvesting by sedimentation induced by high pH.

Microalgae harvesting is a major hurdle for the production of high-value microalgal bioproducts on a large scale. Among harvesting techniques, pH-induced sedimentation stands out as an inexpensive and technically viable method. Nevertheless, there is little information available on the application of this method for microalgae cultivated in wastewater. In this context, the present study investigated the optimization of sedimentation parameters for Chlorella sorokiniana harvesting from wastewater. Parameter optimization was statistically determined by the response surface methodology. The optimal values included a velocity gradient of 250 s-1, mixing time of 10 seconds, and pH of 12, which enabled microalgae harvesting efficiencies of more than 97.8%. These optimal parameters also showed resilience through the physico-chemical variation of the photobioreactor effluent. Furthermore, wastewater quality improved significantly after microalgae harvesting. High removal was found for turbidity (97.9-98.3%), apparent color (92.2-97.2%), total Kjeldhal nitrogen (91.0-94.4%), and total phosphorus (92.8-98.6%). Centrifugation, as the dewatering method, and its operational parameters were also evaluated. Sedimentation followed by centrifugation increased the initial microalgae concentration by about 123 times. This study shows the importance of operational optimization and the results can be used as practical guidelines for microalgae harvesting on a large scale.

Cooking oil-surfactant emulsion in water for harvesting Chlorella vulgaris by sedimentation or flotation.

In this study, a novel harvesting emulsion (HEM) consisting of cooking oil in an aqueous solution of cetyltrimethylammonium bromide (CTAB) was tested for the harvesting of a technologically important microalga, Chlorella vulgaris. The influence of HEM dose, biomass and bovine serum albumin (BSA) (model interferer compound) on harvesting efficiency (E) were studied. The HEM E was over 90% at pH 10 (0.33% (v/v) cooking oil, 6.7 mg/L of CTAB) and 12 (0.13% (v/v) cooking oil, 2.7 mg/L of CTAB). Harvesting efficiencies at pH 4 and 7 were < 73.5% due to the absence of precipitate formation. Bovine serum albumin (10 mg/L) increased the HEM dose necessary to achieve E ˃ 90% by 1.2 (pH 10), and 3 fold (pH 12). By manipulating the dose of HEM and pH, the method of harvesting (flocculation/sedimentation or flotation) was adjustable depending on the technological requirements.

Microalgae harvesting from wastewater by pH modulation and flotation: Assessing and optimizing operational parameters.

Microalgae harvesting is one of the major bottlenecks for the production of high-value microalgal products on a large scale, which encourages investigations of harvesting methods with better cost-benefits. Among these harvesting techniques, flotation stands out as a promising method, however it is still minimally explored when compared to the sedimentation method. In this study, the pH modulation followed by dissolved air flotation (DAF) was tested as a harvesting method for Chlorella sorokiniana cultivated in wastewater. The main aims of this study were to optimize the operational parameters of coagulation (pH, velocity gradient, and mixing time) and flotation (recirculation rate), check their reproducibility and resilience with the variability of wastewater characteristics, and evaluate the final wastewater quality after treatment using an optimized harvesting method. Parameter optimization was carried out using the one-factor-at-a-time method. The optimal parameters were a velocity gradient of 500 s-1, mixing time of 30 s, pH 12, and 20% of recirculation rate. High efficiencies were obtained for C. sorokiniana removal (96.5-97.9%), making it a successful process. Moreover, the photobioreactor effluent quality was also improved significantly after microalgae harvesting, with high nutrient removal (88.6-95.1% of total Kjeldahl nitrogen and 91.8-98.3% of total phosphorus) and organic matter removal (80.5-86.8% of chemical oxygen demand). The results showed the pH modulation and DAF as an effective process for wastewater treatment and biomass harvesting. This study also indicated the importance of operational optimization, not studied until now, in which the achieved results could be potentially applied as practical guidelines for microalgae harvesting on a large scale.

Interference of model wastewater components with flocculation of Chlorella sorokiniana induced by calcium phosphate precipitates.

Amongst harvesting processes, alkaline flocculation stands out as a technically feasible and low cost method. The interference of model wastewater components with alkaline flocculation of Chlorella sorokiniana (pH 8-12), induced by calcium phosphate (CaP) precipitates, was evaluated. Between the compounds tested, inorganic nitrogen, sodium alginate, salinity and algal organic matter had no effect on flocculation efficiency (FE). The negative effect of humic acids, sodium dodecyl sulphate and alkalinity on FE was partial. Bovine serum albumin and bacterial organic matter (BOM) of Escherichia coli showed the strongest disruption of FE. The impact of BOM can be explained by the high protein content (65% of total organic carbon). Proteins, negatively charged at alkaline pH, interrupt microalgae flocculation by preferentially interacting with positively charged CaP precipitates. The simultaneous effects of multiple substances were tested to simulate real wastewater. The results confirm the need to investigate the composition of wastewater prior to alkaline flocculation.