Valorisation of fish-cannery by-products targeting the recovery of ω3 lipids

Over the past years, ω3 fatty acids, namely EPA and DHA, have been recognized as presenting multiple health benefits. Several studies consider fish oil as the most important source of EPA and DHA. Nowadays, canned fish industry plays a very important role in Portuguese economy. However, expansion of this business brought some environmental concerns due to the high amount of by-products generated. Nevertheless, this problem can be substantially reduced by the recovery of some of the by-product components, diminishing its contamination load and simultaneously obtaining value-added products. This study was born from the growing interest in obtaining new sources of lipids rich in ω3 fatty acids, combined with environmental concerns related to the production of wastes from the fish canning industries, rich in these compounds. It thus intends to evaluate lipid extraction methods in liquid by-products from the fish canning industry, aiming to obtain fractions rich in ω3 fatty acids. Additionally, in a biorefining concept, the protein content of the remaining aqueous fractions was also quantified.

Diversification in utilisation of trash fish by gamma irradiation

Radiation pasteurisation enhances the shelf stability of trash fish varieties and enables the grading of fish depending upon the freshness quality. As against the ice-chilled fish which spoils within 8-10 days, exposure to 100 Krad and storage at ice temperature helps in maintaining the quality in Grade I, II or III up to 10, 20 or 25 days respectively. The improvement in quality thus provides scope for greater utilisation of trash fish for various secondary products.

Nutrient Digestibility of Cereal Grain Products and By-products in Extruded Diets for Nile Tilapia

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Restructured products from tilapia industry by products: the effects of tapioca starch and washing cycles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Quality and safety of oils and fats obtained as co-products or by-products of the food chain and destined to animal production

The aim of the first part of this thesis was to evaluate the effect of trans fatty acid- (TFA), contaminant, polycyclic aromatic hydrocarbon (PAH)- and oxidation productenriched diets on the content of TFA and conjugated linoleic acid (CLA) isomers in meat and liver of both poultry and rabbit. The enriched feedings were prepared with preselected fatty co-and by-products that contained low and high levels of TFA (low, palm fatty acid distillate; high, hydrogenated palm fatty acid distillate), environmental contaminants (dioxins and PCBs) (two different fish oils), PAH (olive oil acid oils and pomace olive oil from chemical refining, for low and high levels) and oxidation products (sunflower-olive oil blend before and after frying), so as to obtain single feedings with three enrichment degrees (high, medium and low) of the compound of interest. This experimental set-up is a part of a large, collaborative European project (http://www.ub.edu/feedfat/), where other chemical and health parameters are assessed. Lipids were extracted, methylated with diazomethane, then transmethylated with 2N KOH/methanol and analyzed by GC and silver-ion TLC-GC. TFA and CLA were determined in the fats, the feedings, meat and liver of both poultry and rabbit. In general, the level of TFA and CLA in meat and liver mainly varied according to those originally found in the feeding fats. It must be pointed out, though, that TFA and CLA accumulation was different for the two animal species, as well as for the two types of tissues. The TFA composition of meat and liver changes according to the composition of the oils added to the feeds with some differences between species. Chicken meat with skin shows higher TFA content (2.6–5.4 fold) than rabbit meat, except for the “PAH” trial. Chicken liver shows higher TFA content (1.2–2.1 fold) than rabbit liver, except for the “TRANS” and “PAH” trials. In both chicken and rabbit meats, the TFA content was higher for the “TRANS” trial, followed by the “DIOXIN” trial. Slight differences were found on the “OXIDATION” and “PAH” trends in both types of meats. In both chicken and rabbit livers, the TFA content was higher for the “TRANS” trial, followed by those of the “PAH”, “DIOXIN” and “OXIDATION” trials. This trend, however, was not identical to that of feeds, where the TFA content varied as follows: “TRANS” > “DIOXIN” >“PAH” > “OXIDATION”. In chicken and rabbit meat samples, C18:1 TFA were the most abundant, followed by C18:2 TFA and C18:3 TFA, except for the “DIOXIN” trial where C18:3 TFA > C18:2 TFA. In chicken and rabbit liver samples of the “TRANS” and “OXIDATION” trials, C18:1 TFA were the most abundant, followed by C18:2 TFA and C18:3 TFA, whereas C18:3 TFA > C18:2 in the “DIOXIN” trial. Slight differences were found on the “PAH” trend in livers from both species. The second part of the thesis dealt with the study of lipid oxidation in washed turkey muscle added with different antioxidants. The evaluation on the oxidative stability of muscle foods found that oxidation could be measured by headspace solid phase microestraction (SPME) of hexanal and propanal. To make this method effective, an antioxidant system was added to stored muscle to stop the oxidative processes. An increase in ionic strength of the sample was also implemented to increase the concentration of aldehydes in the headspace. This method was found to be more sensitive than the commonly used thiobarbituric acid reactive substances (TBARs) method. However, after antioxidants were added and oxidation was stopped, the concentration of aldehydes decreased. It was found that the decrease in aldehyde concentration was due to the binding of the aldehydes to muscle proteins, thus decreasing the volatility and making them less detectable.

Chlorine contribution to quantitative structure and activity relationship models of disinfection by -products' quantum chemical descriptors and toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: (1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (E LUMO) via QSAR modelling and analysis; (2) to validate the models by using internal and external cross-validation techniques; (3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl ) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: (1) Linear or Multi-linear Regression (MLR); (2) Partial Least Squares (PLS); and (3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: (1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; (2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; (3) E LUMO are shown to correlate highly with the NCl for several classes of DBPs; and (4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Chlorine Contribution to Quantitative Structure and Activity Relationship Models of Disinfection By-Products' Quantum Chemical Descriptors and Toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: 1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (ELUMO) via QSAR modelling and analysis; 2) to validate the models by using internal and external cross-validation techniques; 3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: 1) Linear or Multi-linear Regression (MLR); 2) Partial Least Squares (PLS); and 3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: 1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; 2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; 3) ELUMO are shown to correlate highly with the NCl for several classes of DBPs; and 4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Effects of rice husk biochar and sugar-mill by-products on methane consumption from two different soils

Methane (CH4) is an important greenhouse gas with a global warming potential (GWP) 25 times greater than carbon dioxide (CO2) that can be produced or consumed in soils depending on environmental conditions and other factors. Biochar application to soils has been shown to reduce CH4 emissions and to increase CH4 consumption. However, the effects of rice husk biochar (RB) have not been thoroughly investigated. Two 60-day laboratory incubation experiments were conducted to investigate the effects of amending two soil types with RB, raw mill mud (MM) and composted mill mud (CM) on soil CH4 consumption and emissions. Soil cores incubated in 1 L glass jars and gas samples were analysed for CH4 using gas chromatography. Average CH4 consumption rates varied from -0.06 to -0.68 g CH4-C( )/ha/d in sandy loam soil and -0.59 to -1.00 g CH4-C/ha/d in clay soil. Application of RB resulted in CH4 uptake of -0.52 to -0.55 g CH4-C/ha/d in sandy loam and -0.76 to -0.91 g CH4-C/ha/d in clay soil. Addition of MM showed low CH4 emissions or consumption at 60% water-filled pore space (WFPS) in both soils. However, at high water contents (>75% WFPS) the application of MM produced high rates of CH4 emissions which were significantly suppressed when RB was added. Cumulative emissions of the MM treatment produced 108.9 g CH4-C/ha at 75% WFPS and 11 459.3 g CH4-C/ha at 90% WFPS in sandy loam soil over a period of 60 days. RB can increase CH4 uptake under low soil water content (SWC) and decrease CH4 emissions under anaerobic conditions. CM expressed more potential to reduce CH4 emissions than those of MM.

Rapid nutrient determination of sugarcane milling by-products using near infrared spectroscopy

This thesis investigates the use of near infrared (NIR) spectroscopic methods for rapid measurement of nutrient elements in mill mud and mill ash. Adoption of NIR-based analyses for carbon, nitrogen, phosphorus, potassium and silicon will allow Australian sugarcane farmers to comply with recent legislative changes, and act within recommended precision farming frameworks. For these analyses, NIR spectroscopic methods surpass several facets of traditional wet chemistry techniques, dramatically reducing costs, required expertise and chemical exposure, while increasing throughput and access to data. Further, this technology can be applied in various modes, including laboratory, at-line and on-line installations, allowing targeted measurement.

Greenhouse gas emissions from sub-tropical agricultural soils after addition of organic by-products

As the cost of mineral fertilisers increases globally, organic soil amendments (OAs) from agricultural sources are increasingly being used as substitutes for nitrogen. However, the impact of OAs on the production of greenhouse gases (CO2 and N2O) is not well understood. A 60-day laboratory incubation experiment was conducted to investigate the impacts of applying OAs (equivalent to 296 kg N ha−1 on average) on N2O and CO2 emissions and soil properties of clay and sandy loam soils from sugar cane production. The experiment included 6 treatments, one being an un-amended (UN) control with addition of five OAs being raw mill mud (MM), composted mill mud (CM), high N compost (HC), rice husk biochar (RB), and raw mill mud plus rice husk biochar (MB). These OAs were incubated at 60, 75 and 90% water-filled pore space (WFPS) at 25°C with urea (equivalent to 200 kg N ha−1) added to the soils thirty days after the incubation commenced. Results showed WFPS did not influence CO2 emissions over the 60 days but the magnitude of emissions as a proportion of C applied was RB < CM < MB < HC

Membrane fractionation technologies for high quality mill sugar and value-added by products - an integrated sugar production process concept model.

Membrane filtration technology has been proven to be a technically sound process to improve the quality of clarified cane juice and subsequently to increase the productivity of crystallisation and the quality of sugar production. However, commercial applications have been hindered because the benefits to crystallisation and sugar quality have not outweighed the increased processing costs associated with membrane applications. An 'Integrated Sugar Production Process (ISPP) Concept Model' is proposed to recover more value from the non-sucrose streams generated by membrane processing. Pilot scale membrane fractionation trials confirmed the technical feasibility of separating high-molecular weight, antioxidant and reducing sugar fractions from cane juice in forms suitable for value recovery. It was also found that up to 40% of potassium salts from the juice can be removed by membrane application while removing the similar amount of water with potential energy saving in subsequent evaporation. Application of ISPP would allow sugar industry to co-produce multiple products and high quality mill sugar while eliminating energy intensive refining processes.