Modern analyses of ancient beer

A recent issue of the Journal of Agriculture and Food Chemistry published an interesting article on chemicals in beers from an 1840s’ shipwreck. 

(photo source: http://www.sci-news.com/, Image credit: John Londesborough et al.) 

In 2010, underwater archaeologists discovered an old schooner south of the Åland Islands at a depth of 50 m in the Baltic Sea. Archeological evidence suggests the shipwreck occurred during the 1840s, but the schooner’s name, its destination and its last port-of-call were not identified. Archeologist brought the cargo consisting of luxury items, including more than 150 bottles of champagne and five bottles that look like typical early 19th century beer bottles to the surface. One of these cracked in the divers’ boat. The liquid that foamed from the cracked bottle looked and, according to the divers, tasted like beer.

Researchers from Finland analyzed two bottles of the beer from the shipwreck  and six bottles of modern  beers (Leffe Brune, Koff Porter, Weihenstephan Hefe Weissbier, Paulaner Hefe Weissbier, Aldaris Porteris Alus, and Olvi Sandels) as reference. The founding provides clues for beer makers to resurrect the flavors of ages past.

The beer samples were degassed by ultrasonification and filtered (0.45 μm). An aliquot (5 μL) was loaded to an HPLC-MS/MS system (high performance liquid chromatography coupled with tandem mass spectrometry) and analyzed for hops related compounds (native or degradation products).

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Sidenote (from Wikipedia): Hops are the female flowers of the hop plant, Humulus lupulus.

Hops are used primarily as a flavoring and stability agent in beer. Hops impart a bitter, tangy flavor to beer. Hops have antibacterial effect that favors the activity of brewer's yeast over less desirable microorganisms and for many purported benefits such as balancing the sweetness of the malt with bitterness and contributing a variety of desirable flavors
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Above: Chemical structures of bitter chemicals identified in hops and freshly brewed beer; Below: Chemical structures of bitter chemicals identified in aged beer (Source: J. Agric. Food Chem. 2010, 58, 7930–7939)
Based on the chemical fingerprint in the beer, the two bottles of ancient beer were identified as two different kind of beer.  One was more strongly hopped than the other. 

High levels of organic acids, carbonyl compounds, and glucose indicated extensive bacterial and enzyme activity during aging. However, concentrations of yeast-derived flavor compounds were similar to those of modern beers, except that 3-methylbutyl acetate

was unusually low in both beers and 2-phenylethanol

and possibly 2-phenylethyl acetate

were unusually high in one beer. Concentrations of phenolic compounds were similar to those in modern lagers and ales

Besides hops related chemicals, the researchers also analyzed other chemical components in the ancient beer. Compared to typical modern lagers and ales, ethanol contents of the shipwreck beers were low (2.8-3.2%). Glycerol and ethanol had a ratio of 4.5% for both shipwreck beers, which is typical for a yeast fermentation product. Both beers were acidic, but their pH were ~1 below modern values. The color strengths were in the range of modern ales and lagers, and much lower than porters or stouts. Possibly been oxidized after over the 170 years, sulfur dioxide was not detected in shipwreck beers. Protein levels were very low in both beers.

References: 

• John Londesborough, Michael Dresel, Brian Gibson, Riikka Juvonen, Ulla Holopainen, Atte Mikkelson, Tuulikki Seppänen-Laakso, Kaarina Viljanen, Hannele Virtanen, Arvi Wilpola, Thomas Hofmann, and Annika Wilhelmson J. Agric. Food Chem. 2015, 63, 2525−2536 DOI: 10.1021/jf5052943 Analysis of Beers from an 1840s’ Shipwreck 2015, 63 (9), pp 2525–2536
• Gesa Haseleu, Annika Lagemann, Andreas Stephan, Daniel Intelmann, Andreas Dunkel and Thomas Hofmann. Quantitative Sensomics Profiling of Hop-Derived Bitter Compounds Throughout a Full-Scale Beer Manufacturing Process. J. Agric. Food Chem., 2010, 58 (13), pp 7930–7939 DOI: 10.1021/jf101326v
• http://www.sci-news.com/othersciences/chemistry/science-beer-1840s-shipwreck-finland-02567.html

Purifying urban air with pavement containing titanium dioxide

A recent study published in the journal of Atmospheric Environment by Folli et al. demonstrated the effectiveness of cleaning NOx in urban air via photocatalytic oxidation using titanium dioxide as semiconductor photocatalyst added to pavement.

(source of image: www.mapfre.com)

The advantage of such technology is that photocatalystic oxidation only requires sunlight, existing oxygen and water in air. Therefore, remediation is continuous in day light.

In this study, researchers conducted a year-long field test in the city of Copenhagen. They employed two continuous air monitoring stations, one in the area with photocatalytic concrete pavers and the second one in the area without photocatalytic concrete and assessed the effectiveness of TiO2 containing pavement in removing NOx in the air.

The study indicates that a monthly abatement of NO was around 22% in the summer months;
NO noon abatement was >45% at the summer solstice, which corresponded to NOx noon abatement > 30%.

Personally, I think such technology is very promising although more research work needs to be done. Research questions worth to be addressed include but not limited to

• Does the technology also has the benefit of degrade other toxic chemicals in urban air such as polycyclic aromatic compounds?

• What's the over all benefit of such technology if widely used in urban pavement and building walls and how does the benefit of removal toxic chemicals compared to the cost. 

• What degradation products can be generated and how do they affect urban air and environmental quality? 

 In addition to the article by Folli et al. mentioned above http://dx.doi.org/10.1016/j.atmosenv.2015.02.025, the following articles on the removal of pollutants by adding TiO2 in cement are also informative on this topic.

• Folli, J.Z. Bloh, M. Strøm, T. Pilegaard Madsen, T. Henriksen, D.E. Macphee Efficiency of solar-light-driven TiO2 photocatalysis at different latitudes and seasons. Where and when does TiO2 really work? J. Phys. Chem. Lett., 5 (5) (2014), pp. 830–832 http://dx.doi.org/10.1021/jz402704n

• J. Ângelo, L. Andrade, L.M. Madeira, A. Mendes An overview of photocatalysis phenomena applied to NOx abatement J. Environ. Manag., 129 (2013), pp. 522–539 http://dx.doi.org/10.1016/j.jenvman.2013.08.006

• M.M. Ballari, H.J.H. Brouwers Full scale demonstration of air-purifying pavement J. Hazard. Mater., 254–255 (2) (2013), pp. 406–414 URL http://dx.doi.org/10.1016/j.jhazmat.2013.02.012

Chemistry of skin lipids

Human body is covered with skin surface lipids. The majority of skin lipids are sebaceous lipids which are secreted by sebaceous glands.  Epidermis also produce a tiny fraction of total extractable surface lipid. On skin areas rich in sebaceous glands such as forehead,  epidermal  lipids are 5-10 µg/cm3 compared with 150-300 µg of sebaceous lipids.

Chemicals that constitute skin surface lipids include non-polar lipids, mainly triglycerides, wax esters, squalene, fatty acids and smaller amounts of cholesterol, cholesterol esters and diglycerides

Carbon-carbon double bonds involve in many of these constituents.  Such chemicals are readily to react with ozone. On a molar basis, squalene is responsible for roughly 50% of the unsaturated carbon bonds in skin surface lipids. Hence, squalene is the most important individual constituent in terms of ozone consumption.

The fractional contribution and  levels of skin lipids change with human ages. For example, the amounts of omega-7 unsaturated fatty acids

 have been found to increase with increasing age

Reactions between ozone and skin lipids generally follow the Criegee mechanism

(Youtube education material on Criegee mechanism of ozonolysis)

The ozone-skin lipids reaction products cover a range of volatility. These more volatile products are found primarily in the gas-phase while the less volatile primary and secondary products are found primarily in the condensed phase (e.g., skin, hair, clothing surfaces,  airborne particles,surface film).

Based on the Criegee mechanism, the ozone/squalene reaction is anticipated to produce aldehydes and organic acids with 27, 22, or 17 carbon atoms and five, four, or three double bonds, respectively and hydrogen peroxide (H2O2), organic peroxides (ROOR) , and short-lived highly reactive products including hydroxyl (OH.), hydroperoxyl (HOO.), and alkyl peroxyl radicals (ROO.). These radicals will react with squalene and primary and secondary products producing additional carbonyls, dicarbonyls, and hydroxycarbonyls.  Given the number of double bonds in these less volatile products, they themselves readily react with ozone to generate still more products.

The reaction could generate products with high hydrophilicity, which increases their transdermal penetration and redox activity. Such products from ozonolysis could pose potential risk  to human health.

image source: http://www.cdc.gov/niosh/topics/skin/

Some of the primary and secondary ozone/lipids reaction products can condense on existing particles or nucleate to form new particles or secondary organic aerosols (SOA) with size ~10-1000 nm. Based on chamber experiments, the size of SOA formed depends on ozone concentrations with larger size at higher O3 concentrations. 

The reaction of O3 with lipids at skin surface involves the deposition of ozone to skin surface and the chemical reaction.  Various studies suggest the actual reaction is very fast and the overall rate limit step is the deposition of ozone to the surface. 


References and further information: 

• Weschler CJ, Roles of the human occupant in indoor chemistry. Indoor Air. 2015 http://dx.doi.org/10.1111/ina.12185
• Apostolos Pappas. Epidermal surface lipids.2009 1(2): 72–76
  http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2835894/pdf/de0102_0072.pdf

Firework as a source of perchlorate-a contaminant of emerging concern

Potassium Perchlorate (KClO4) as an oxidizer is commonly used in fireworks to produce temperatures of 1700 to 2000°C. Such high temperature make it possible to excite the electrons surrounding the nuclei of metal atoms and when the absorbed energy is emitted, different atoms give out specific colors. 

Firework is an important source of perchlorate to aquatic environment. Monitoring data show over four percent of public water systems have detected perchlorate.  In a human biomonitoring campaign, perchlorate was found in all human urine samples collected from the U.S. The chemical was also found in cow's milk in California with an average level of 1.3 µg/L, which may have entered the cows through feeding on crops that had exposure to water containing perchlorates. Studies have indicated that perchlorate can disrupt the thyroid’s ability to produce hormones needed for normal growth and development.

Because of the adverse effect on the health and frequent detection in public water systems at levels causing a public health concern, the U.S. Environmental Protection Agency issued a "regulatory determination" in 2011 that perchlorate meets the Safe Drinking Water Act criteria for regulation as a contaminant. Prior to issuance of its regulatory determination, the U.S. EPA issued a recommended Drinking Water Equivalent Level (DWEL) for perchlorate of 24.5 µg/L. Such regulation provides
opportunity for health risk reduction for the between 5.2 and 16.6 million people who may be
served drinking water containing perchlorate.

References and more to read:

http://water.epa.gov/drink/contaminants/unregulated/perchlorate.cfm
http://water.epa.gov/drink/contaminants/unregulated/upload/FactSheet_PerchlorateDetermination.pdf
http://pubs.acs.org/doi/abs/10.1021/es504444e
Blount, B. C.; Valentin-Blasini, L.; Osterloh, J. D.; Mauldin, J. P.; Pirkle, J. L. Perchlorate exposure of the US Population, 2001−2002. J. Exposure Sci. Environ. Epidemiol. 2007, 17 (4), 400−407.