Bioremediation of phosphates in seawater: approach for recirculating marine aquaculture effluents

Marine Recirculating Aquaculture Systems (RAS) produce great volume of wastewater, which may be reutilized/recirculated or reutilized after undergoing different treatment/remediation methods, or partly discharged into neighbour water-bodies (DWW). Phosphates, in particular, are usually accumulated at high concentrations in DWW, both because its monitoring is not compulsory for fish production since it is not a limiting parameter, and also because there is no specific treatment so far developed to remove them, especially in what concerns saltwater effluents. As such, this work addresses two main scientific questions. One of them regards the understanding of the actual (bio)remediation methods applied to effluents produced in marine RAS, by identifying their advantages, drawbacks and gaps concerning their exploitation in saltwater effluents. The second one is the development of a new, innovative and efficient method for the treatment of saltwater effluents that potentially fulfil the gaps identified in the conventional treatments. Thereby, the aims of this thesis are: (i) to revise the conventional treatments targeting major contaminants in marine RAS effluents, with a particular focus on the bioremediation approaches already conducted for phosphates; (ii) to characterize and evaluate the potential of oyster-shell waste collected in Ria de Aveiro as a bioremediation agent of phosphates spiked into artificial saltwater, over different influencing factors (e.g., oyster-shell pre-treatment through calcination, particle size, adsorbent concentration). Despite the use of oyster-shells for phosphorous (P) removal has already been applied in freshwater, its biosorptive potential for P in saltwater was never evaluated, as far as I am aware. The results herein generated showed that NOS is mainly composed by carbonates, which are almost completely converted into lime (CaO) after calcination (COS). Such pre-treatment allowed obtaining a more reactive material for P removal, since higher removal percentages and adsorption capacity was observed for COS. Smaller particle size fractions for both NOS and COS samples also increased P removal. Kinetic models showed that NOS adsorption followed, simultaneously, Elovich and Intraparticle Difusion kinetic models, suggesting that P removal is both a diffusional and chemically rate-controlled process. The percentage of P removal by COS was not controlled by Intraparticle Diffusion and the Elovich model was the kinetic model that best fitted phosphate removal. This work demonstrated that waste oyster-shells, either NOS or COS, could be used as an effective biosorbent for P removal from seawater. Thereby, this biomaterial can sustain a cost-effective and eco-friendly bioremediation strategy with potential application in marine RAS.

Assessment of seawater pollution by heavy metals (lead & cadmium) in the Qeshm rocky shore: use of the sea urchin, Echinometra mathaei, as a bioindicator

The general purpose of this study is to investigate the degree of heavy metal accumulation in hard and soft tissue of sea urchin, and determining these tissues as the most suitable bioindicator for lead and cadmium in the environment of the sampling stations. The way of doing this assessment was MOOPAM. Samples were prepared and classified according to sea urchin organ (soft tissue, hard tissue, Tube feet, Test, Lantern Structure and spines) and then lead and cadmium were measured in them. Result of this study shows that hard tissue is a better index of lead and cadmium than soft tissue. The result of bioaccumulation of lead in the related tissue was found to be in the following order: Soft tissue=21, hard tissue=28.1, Test=20.8, Lantern Structure=20.5 and spines=23.9. The result of bioaccumulation of cadmium in the related tissue was found to be in the following order: Soft tissue=9. 7, hard tissue=5.01, Test=4.2, Lantern Structure=4.06 and spines=5.53.

Fukushima-derived radionuclides in sediments of the Japanese Pacific Ocean coast and various Japanese water samples (seawater, tap water, and coolant water of Fukushima Daiichi reactor unit 5)

We investigated Ocean sediments and seawater from inside the Fukushima exclusion zone and found radiocesium (134Cs and 137Cs) up to 800 Bq kg-1 as well as 90Sr up to 5.6 Bq kg-1. This is one of the first reports on radiostrontium in sea sediments from the Fukushima exclusion zone. Seawater exhibited contamination levels up to 5.3 Bq kg-1 radiocesium. Tap water from Tokyo from weeks after the accident exhibited detectable but harmless activities of radiocesium (well below the regulatory limit). Analysis of the Unit 5 reactor coolant (finding only 3H and even low 129I) leads to the conclusion that the purification techniques for reactor coolant employed at Fukushima Daiichi are very effective.

Thermal and exergy analysis for evaluation and optimization of performance of cooling towers for fresh water and seawater

In this study, thermal, exergetic analysis and performance evaluation of seawater and fresh wet cooling tower and the effect of parameters on its performance is investigated. With using of energy and mass balance equations, experimental results, a mathematical model and EES code developed. Due to lack of fresh water, seawater cooling is interesting choice for future of cooling, so the effect of seawater in the range of 1gr/kg to 60gr/kg for salinity on the performance characteristics like air efficiency, water efficiency, output water temperature of cooling tower, flow of the exergy, and the exergy efficiency with comparison with fresh water examined. Decreasing of air efficiency about 3%, increasing of water efficiency about 1.5% are some of these effects. Moreover with formation of fouling the performance of cooling tower decreased about 15% which this phenomena and its effects like increase in output water temperature and tower excess volume has been showed and also accommodate with others work. Also optimization for minimizing cost, maximizing air efficiency, and minimizing exergy destruction has been done, results showed that optimization on minimizing the exergy destruction has been satisfy both minimization of the cost and the maximization of the air efficiency, although it will not necessarily permanent for all inputs and optimizations. Validation of this work is done by comparing computational results and experimental data which showed that the model have a good accuracy.

Corrosion of stainless steel components in seawater reverse osmosis desalination plants-investigations on adapted internal cathodic protection

Stainless steel is widely used in seawater reverse osmosis units (SWRO) for both good mechanical and corrosion resistance properties. However, many corrosion failures of stainless steel in SWRO desalination units have been reported. These failures may often be attributed to un-adapted stainless steel grade selection and/or to the particular aggressive seawater conditions in "warm" regions (high ambient temperature, severe biofouling, etc.). Cathodic protection (CP) is a well-known efficient system to prevent corrosion of metallic materials in seawater. It is successfully used in the oil and gas industry to protect carbon steel structures exposed in open-sea. However, the specific service conditions of SWRO units may seriously affect the efficiency of such anti-corrosion system (high flow rates, large stainless steel surfaces affected by biofouling, confinement limiting protective cathodic current flow, etc.). Hence, CP in SWRO units should be considered with special care and modeling appears as useful tool to assess an appropriate CP design. However, there is a clear lack of CP data that could be transposed to SWRO service conditions (i.e. stainless steel, effect of biofouling, high flow rate, etc.). From this background a Join Industry Program was initiated including laboratory exposures, field measurements in a full scale SWRO desalination plant, and modeling work using PROCOR software. The present paper reviews the main parameters affecting corrosion of stainless steel alloys in seawater reverse osmosis units. CP on specific stainless steel devices was investigated in order to assess its actual efficiency for SWRO units. Severe environmental conditions were intentionally used to promote corrosion on the tested stainless steel products in order to evaluate the efficiency of CP. The study includes a modeling work aiming at predicting and designing adapted CP protection to modeled stainless steel units. An excellent correlation between modeling work and field measurements was found.

Antimicrobial resistance of heterotrophic marine bacteria isolated from seawater and sands of recreational beaches with different organic pollution levels in southeastern Brazil: evidences of resistance dissemination

Antimicrobial resistance of marine heterotrophic bacteria to different antimicrobials agents were evaluated in seawater, dry and wet sands from three marine recreational beaches with different pollution levels. In all studied beaches, the greatest frequencies of resistance were found in relation to penicillin. on Gonzaguinha, the most polluted beach, 72.3% of all isolated strains showed simple resistance, whilst 8.33% had multiple resistance. The values found on Ilha Porchat beach, were 70.8% and 6.9% for simple and multiple resistances, respectively. on GuaraA(0), the less polluted beach, only 35.3% of isolated strains had simple resistance. Multiple resistance was not observed. While samples from Gonzaguinha and Ilha Porchat beach showed isolated strains resistant to seven and six different antimicrobial agents, respectively, samples from GuaraA(0) beach were resistant only to penicillin and erytromicin. The positive correlations obtained between the degree of seawater contamination and frequency and variability of bacterial resistance indicate that polluted marine recreational waters and sands are sources of resistant bacteria contributing thus, to the dissemination of bacterial resistance.

Determination of the Side-Reaction Coefficient of Desferrioxamine B in Trace-Metal-Free Seawater

Partial funding for open access provided by the UMD Libraries' Open Access Publishing Fund.

Brucite Microbialites in Living Coral Skeletons: Indicators of Extreme Microenvironments in Shallow-Marine Settings

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies.

Earliest diagenesis in scleractinian coral skeletons : implications for palaeoclimate-sensitive geochemical archives

Live-collected samples of four common reef building coral genera (Acropora, Pocillopora, Goniastrea, Porites) from subtidal and intertidal settings of Heron Reef, Great Barrier Reef, show extensive early marine diagenesis where parts of the coralla less than 3 years old contain abundant macro- and microborings and aragonite, high-Mg calcite, low-Mg calcite, and brucite cements. Many types of cement are associated directly with microendoliths and endobionts that inhabit parts of the corallum recently abandoned by coral polyps. The occurrence of cements that generally do not precipitate in normal shallow seawater (e.g., brucite, low-Mg calcite) highlights the importance of microenvironments in coral diagenesis. Cements precipitated in microenvironments may not reXect ambient seawater chemistry. Hence, geochemical sampling of these cements will contaminate trace-element and stable-isotope inventories used for palaeoclimate and dating analysis. Thus, great care must be taken in vetting samples for both bulk and microanalysis of geochemistry. Visual inspection using scanning electron microscopy may be required for vetting in many cases.

Comparison of molecular markers to detect fresh sewage in environmental waters

Human-specific Bacteroides HF183 (HS-HF183), human-specific Enterococci faecium esp (HS-esp), human-specific adenoviruses (HS-AVs) and human-specific polyomaviruses (HS-PVs) assays were evaluated in freshwater, seawater and distilled water to detect fresh sewage. The sewage spiked water samples were also tested for the concentrations of traditional fecal indicators (i.e., Escherichia coli, enterococci and Clostridium perfringens) and enteric viruses such as enteroviruses (EVs), sapoviruses (SVs), and torquetenoviruses (TVs). The overall host-specificity of the HS-HF183 marker to differentiate between humans and other animals was 98%. However, the HS-esp, HS-AVs and HS-PVs showed 100% hostspecificity. All the human-specific markers showed >97% sensitivity to detect human fecal pollution. E. coli, enterococci and, C. perfringens were detected up to dilutions of sewage 10_5, 10_4 and 10_3 respectively.HS-esp, HS-AVs, HS-PVs, SVs and TVs were detected up to dilution of sewage 10_4 whilst EVs were detected up to dilution 10_5. The ability of the HS-HF183 marker to detect freshsewagewas3–4 orders ofmagnitude higher than that of the HS-esp and viral markers. The ability to detect fresh sewage in freshwater, seawater and distilled water matrices was similar for human-specific bacterial and viral marker. Based on our data, it appears that human-specific molecular markers are sensitive measures of fresh sewage pollution, and the HS-HF183 marker appears to be the most sensitive among these markers in terms of detecting fresh sewage. However, the presence of the HS-HF183 marker in environmental waters may not necessarily indicate the presence of enteric viruses due to their high abundance in sewage compared to enteric viruses. More research is required on the persistency of these markers in environmental water samples in relation to traditional fecal indicators and enteric pathogens.

Thermal decomposition of Bayer precipitates formed at varying temperatures

Bayer hydrotalcites prepared using the seawater neutralisation (SWN) process of Bayer liquors are characterised using X-ray diffraction and thermal analysis techniques. The Bayer hydrotalcites are synthesised at four different temperatures (0, 25, 55, 75 °C) to determine the effect on the thermal stability of the hydrotalcite structure, and to identify other precipitates that form at these temperatures. The interlayer distance increased with increasing synthesis temperature, up to 55 °C, and then decreased by 0.14 Å for Bayer hydrotalcites prepared at 75 °C. The three mineralogical phases identified in this investigation are; 1) Bayer hydrotalcite, 2), calcium carbonate species, and 3) hydromagnesite. The DTG curve can be separated into four decomposition steps; 1) the removal of adsorbed water and free interlayer water in hydrotalcite (30 – 230 °C), 2) the dehydroxylation of hydrotalcite and the decarbonation of hydrotalcite (250 – 400 °C), 3) the decarbonation of hydromagnesite (400 – 550 °C), and 4) the decarbonation of aragonite (550 – 650 °C).

Use of hydrotalcites for the removal of toxic anions from aqueous solutions

The removal of toxic anions has been achieved using hydrotalcite via two methods: (1) coprecipitation and (2) thermal activation. Hydrotalcite formed via the coprecipitation method, using solutions containing arsenate and vanadate up to pH 10, are able to remove more than 95% of the toxic anions (0.2 M) from solution. The removal of toxic anions in solutions with a pH of >10 reduces the removal uptake percentage to 75%. Raman spectroscopy observed multiple A1 stretching modes of V−O and As−O at 930 and 810 cm−1, assigned to vanadate and arsenate, respectively. Analysis of the intensity and position of the A1 stretching modes helped to identify the vanadate and arsenate specie intercalated into the hydrotalcite structure. It has been determined that 3:1 hydrotalcite structure predominantly intercalate anions into the interlayer region, while the 2:1 and 4:1 hydrotalcite structures shows a large portion of anions being removed from solution by adsorption processes. Treatment of carbonate solutions (0.2 M) containing arsenate and vanadate (0.2 M) three times with thermally activated hydrotalcite has been shown to remove 76% and 81% of the toxic anions, respectively. Thermally activated hydrotalcite with a Mg:Al ratio of 2:1, 3:1, and 4:1 have all been shown to remove 95% of arsenate and vanadate (25 ppm). At increased concentrations of arsenate and vanadate, the removal uptake percentage decreased significantly, except for the 4:1 thermally activated hydrotalcite. Thermally activated Bayer hydrotalcite has also been shown to be highly effective in the removal of arsenate and vanadate. The thermal activation of the solid residue component (red mud) removes 30% of anions from solution (100 ppm of both anions), while seawater-neutralized red mud removes 70%. The formation of hydrotalcite during the seawater neutralization process removes anions via two mechanisms, rather than one observed for thermally activated red mud.

A two-Dimensional finite volume method for variable density flow and solute transport through saturated-unsaturated media

Extensive groundwater withdrawal has resulted in a severe seawater intrusion problem in the Gooburrum aquifers at Bundaberg, Queensland, Australia. Better management strategies can be implemented by understanding the seawater intrusion processes in those aquifers. To study the seawater intrusion process in the region, a two-dimensional density-dependent, saturated and unsaturated flow and transport computational model is used. The model consists of a coupled system of two non-linear partial differential equations. The first equation describes the flow of a variable-density fluid, and the second equation describes the transport of dissolved salt. A two-dimensional control volume finite element model is developed for simulating the seawater intrusion into the heterogeneous aquifer system at Gooburrum. The simulation results provide a realistic mechanism by which to study the convoluted transport phenomena evolving in this complex heterogeneous coastal aquifer.

The organic fraction of bubble-generated, accumulation mode Sea Spray Aerosol (SSA)

Recent studies have detected a dominant accumulation mode (~100 nm) in the Sea Spray Aerosol (SSA) number distribution. There is evidence to suggest that particles in this mode are composed primarily of organics. To investigate this hypothesis we conducted experiments on NaCl, artificial SSA and natural SSA particles with a Volatility-Hygroscopicity-Tandem-Differential-Mobility-Analyser (VH-TDMA). NaCl particles were atomiser generated and a bubble generator was constructed to produce artificial and natural SSA particles. Natural seawater samples for use in the bubble generator were collected from biologically active, terrestrially-affected coastal water in Moreton Bay, Australia. Differences in the VH-TDMA-measured volatility curves of artificial and natural SSA particles were used to investigate and quantify the organic fraction of natural SSA particles. Hygroscopic Growth Factor (HGF) data, also obtained by the VH-TDMA, were used to confirm the conclusions drawn from the volatility data. Both datasets indicated that the organic fraction of our natural SSA particles evaporated in the VH-TDMA over the temperature range 170–200°C. The organic volume fraction for 71–77 nm natural SSA particles was 8±6%. Organic volume fraction did not vary significantly with varying water residence time (40 secs to 24 hrs) in the bubble generator or SSA particle diameter in the range 38–173 nm. At room temperature we measured shape- and Kelvin-corrected HGF at 90% RH of 2.46±0.02 for NaCl, 2.35±0.02 for artifical SSA and 2.26±0.02 for natural SSA particles. Overall, these results suggest that the natural accumulation mode SSA particles produced in these experiments contained only a minor organic fraction, which had little effect on hygroscopic growth. Our measurement of 8±6% is an order of magnitude below two previous measurements of the organic fraction in SSA particles of comparable sizes. We stress that our results were obtained using coastal seawater and they can’t necessarily be applied on a regional or global ocean scale. Nevertheless, considering the order of magnitude discrepancy between this and previous studies, further research with independent measurement techniques and a variety of different seawaters is required to better quantify how much organic material is present in accumulation mode SSA.