Analysis of the organic matter associated to sea salt : definition of potential molecular markers based on the volatile composition and presence of glycosidic derivatives and polysaccharides

Sea salt is a natural product obtained from the evaporation of seawater in saltpans due to the combined effect of wind and sunlight. Nowadays, there is a growing interest for protection and re-valorisation of saltpans intrinsically associated to the quality of sea salt that can be evaluated by its physico-chemical properties. These man-made systems can be located in different geographical areas presenting different environmental surroundings. During the crystallization process, organic compounds coming from these surroundings can be incorporated into sea salt crystals, influencing their final composition. The organic matter associated to sea salt arises from three main sources: algae, surrounding bacterial community, and anthropogenic activity. Based on the hypothesis that sea salt contains associated organic compounds that can be used as markers of the product, including saltpans surrounding environment, the aim of this PhD thesis was to identify these compounds. With this purpose, this work comprised: 1) a deep characterisation of the volatile composition of sea salt by headspace solid phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME/GCGC–ToFMS) methodology, in search of potential sea salt volatile markers; 2) the development of a methodology to isolate the polymeric material potentially present in sea salt, in amounts that allow its characterisation in terms of polysaccharides and protein; and 3) to explore the possible presence of triacylglycerides. The high chromatographic resolution and sensitivity of GC×GC–ToFMS enabled the separation and identification of a higher number of volatile compounds from sea salt, about three folds, compared to unidimentional chromatography (GC–qMS). The chromatographic contour plots obtained revealed the complexity of marine salt volatile composition and confirmed the relevance of GC×GC–ToFMS for this type of analysis. The structured bidimentional chromatographic profile arising from 1D volatility and 2D polarity was demonstrated, allowing more reliable identifications. Results obtained for analysis of salt from two locations in Aveiro and harvested over three years suggest the loss of volatile compounds along the time of storage of the salt. From Atlantic Ocean salts of seven different geographical origins, all produced in 2007, it was possible to identify a sub-set of ten compounds present in all salts, namely 6-methyl-5-hepten-2-one, 2,2,6-trimethylcyclohexanone, isophorone, ketoisophorone, β-ionone-5,6-epoxide, dihydroactinidiolide, 6,10,14-trimethyl-2-pentadecanone, 3-hydroxy-2,4,4-trimethylpentyl 2-methylpropanoate, 2,4,4-trimethylpentane-1,3-diyl bis(2-methylpropanoate), and 2-ethyl-1-hexanol. These ten compounds were considered potential volatile markers of sea salt. Seven of these compounds are carotenoid-derived compounds, and the other three may result from the integration of compounds from anthropogenic activity as metabolites of marine organisms. The present PhD work also allowed the isolation and characterisation, for the first time, of polymeric material from sea salt, using 16 Atlantic Ocean salts. A dialysis-based methodology was developed to isolate the polymeric material from sea salt in amounts that allowed its characterisation. The median content of polymeric material isolated from the 16 salts was 144 mg per kg of salt, e.g. 0.014% (w/w). Mid-infrared spectroscopy and thermogravimetry revealed the main occurrence of sulfated polysaccharides, as well as the presence of protein in the polymeric material from sea salt. Sea salt polysaccharides were found to be rich in uronic acid residues (21 mol%), glucose (18), galactose (16), and fucose (13). Sulfate content represented a median of 45 mol%, being the median content of sulfated polysaccharides 461 mg/g of polymeric material, which accounted for 66 mg/kg of dry salt. Glycosidic linkage composition indicates that the main sugar residues that could carry one or more sulfate groups were identified as fucose and galactose. This fact allowed to infer that the polysaccharides from sea salt arise mainly from algae, due to their abundance and composition. The amino acid profile of the polymeric material from the 16 Atlantic Ocean salts showed as main residues, as medians, alanine (25 mol%), leucine (14), and valine (14), which are hydrophobic, being the median protein content 35 mg/g, i.e. 4,9 mg per kg of dry salt. Beside the occurrence of hydrophobic volatile compounds in sea salt, hydrophobic non-volatile compounds were also detected. Triacylglycerides were obtained from sea salt by soxhlet extraction with n-hexane. Fatty acid composition revealed palmitic acid as the major residue (43 mol%), followed by stearic (13), linolenic (13), oleic (12), and linoleic (9). Sea salt triacylglycerides median content was 1.5 mg per kg of dry salt. Both protein and triacylglycerides seem to arise from macro and microalgae, phytoplankton and cyanobacteria, due to their abundance and composition. Despite the variability resulting from saltpans surrounding environment, this PhD thesis allowed the identification of a sea salt characteristic organic compounds profile based on volatile compounds, polysaccharides, protein, and triacylglycerides.

Speech of Mr. C. G. Memminger, on the question of rechartering the bank of the state of South Carolina: delivered in the House of Representatives, December 9, 1848

This speech by Mr. Memminger offers resolutions on the issue of rechartering the bank of the state of South Carolina. The issues presented are the Bank of the State is founded on an erroneous policy, unwise for a state to engage in banking, not practical to recharter the Bank of the State and a special committee of each house should be appointed to advise how to carry out these resolutions at the next session.

Address of Mr. C. G. Memminger, to the people of St. Phillip's and St. Michael's, in relation to the Bank of the State : containing facts and arguments in favor of the bill, which he was prevented from presenting before the House, at the last session of the Legislature

This document contains the facts and arguments in favor of the bill, which he was prevented from presenting before the House of Representatives at the last session of the legislature.

Deep-Sea ecosystem model of the Condor seamount

Dissertação de Mestrado, Estudos Integrados dos Oceanos, 25 de Julho 2013, Universidade dos Açores.

A label-free DNA aptamer-based impedance biosensor for the detection of E. coli outer membrane proteins

A label-free DNA aptamer-based impedance biosensor for the detection of E. coli outer membrane proteins (OMPs) was developed. Two single stranded DNA sequences were tested as recognition elements and compared. The aptamer capture probes were immobilized, with and without 6-mercapto-1-hexanol (MCH) on a gold electrode. Each step of the modification process was characterized by Faradaic impedance spectroscopy (FIS). A linear relationship between the electron-transfer resistance (Ret) and E. coli OMPs concentration was demonstrated in a dynamic detection range of 1 × 10−7–2 × 10−6 M. Moreover, the aptasensor showed selectivity despite the presence of other possible water contaminates and could be regenerated under low pH condition. The developed biosensor shows great potential to be incorporated in a biochip and used for in situ detection of E. coli OMPs in water samples.

Bank of Canada Records, 1958-1989

The Bank of Canada first introduced Canada Savings Bonds during the First and Second World Wars. At the time, they were known as War Savings Certificates and Victory Bonds and were used to fund the war effort. In 1946, Canada Savings Bonds were used as part of Canada’s Postwar Financing Program. At that time, the government also introduced the sale of bonds through payroll deduction. Canada Savings Bonds proved to be very popular, providing investors with a convenient, flexible and safe investment. Over time the bonds failed to remain competitive with other low-risk investment options, and the high cost of administering the program called into question its relevance. An independent report commissioned by the government in 2004 recommended that the bonds be phased out, however, the government decided to keep the program and make some revisions. As of 2012, Canada Savings Bonds are available exclusively through the payroll savings program, while Canada Premium Bonds (introduced in 1998) are available through financial institutions, dealers and by phone.

Royal Bank of Canada records, 1973-1977

In 1973, the Royal Bank of Canada began construction on a new office in downtown Toronto known as the Royal Bank Plaza. The $100 million construction project consisted of two triangular office towers linked by a glass-enclosed banking hall. In addition to housing the Royal Bank of Canada’s Ontario headquarters, the Plaza included a two-level shopping concourse with restaurants and boutiques, as well as office space available for lease. The Plaza officially opened on March 10, 1977.

Niagara Falls (Image from Eastern District of Pennsylvania Clerks Office)

The caption below reads "Entered according to Act of Congress in the year 1854 by F. Langenheim in the Clerks office of the district Court for the Eastern district of Pennsylvania".

Canadian Bank of Commerce (vinyl cover), St. Catharines bank book of Welland D. Woodruff Esq.

Canadian Bank of Commerce (vinyl cover), St. Catharines bank book of Welland D. Woodruff Esq., 1915-1917.

Memoranda booklet (soft cover) compliments of the Canadian Bank of Commerce, St. Catharines Branch

Memoranda booklet (soft cover) compliments of the Canadian Bank of Commerce, St. Catharines Branch. Only one page has writing on it. It appears to be a shopping list, n.d.

Indenture of assignment of mortgage between Executors of the Zimmerman Estate and the Bank of Upper Canada

Indenture of assignment of mortgage between Executors of the Zimmerman Estate and the Bank of Upper Canada regarding Lot no. 4 in block O in the Town of Elgin – instrument no. 6360, May 14, 1858.

Letter to William Dickson of Galt from the cashier of the Bank of Upper Canada

Letter to William Dickson of Galt from the cashier of the Bank of Upper Canada, Toronto, Ontario. This letter informs Mr. Dickson that he has received a bonus on his shares of the Old Stock on the Bank of Upper Canada due to an act that was passed by legislature (3 pages, printed), Jan. 6, 1855.