By Heather Rock Woods
Henry VIII’s warship, the Mary Rose, wreaked havoc on the French navy for 34 years until she was wrecked in 1545. Salvaged from the sea in 1982, she now rests in the Mary Rose Museum in Portsmouth, England. Pieces of her helm, however, recently traveled to Menlo Park, California and Grenoble, France where intense x-rays pierced the wood analyzing the sulfur and iron within.
A research team, led by University of Stockholm Professor Magnus Sandström, and including Mary Rose chief scientist Mark Jones, used synchrotron x-rays from SSRL and the European Synchrotron Radiation Facility (ESRF). The prevalence of sulfur and iron in the oak timbers poses long-term preservation challenges, but the new information can also help to overcome the threats.
The results, published September 26 in Proceedings of the National Academy of Sciences, indicate the surviving wood contains two tons of sulfur in different forms, uniformly distributed within the 280-ton hull. Over time, sulfur can convert to sulfuric acid, which could slowly degrade the wood until its stability is lost. Sandström’s earlier work, also done at SSRL, on the Swedish warship Vasa (under water for 333 years) showed that the accumulation of sulfur within shipwrecks in seawater is common.
Complementary experiments at SSRL and ESRF revealed the quantities, locations and chemical state of sulfur and iron in the Mary Rose’s wood, zooming in on their structures on an atomic scale. Researchers found the highest concentrations of sulfur are in areas between the wood cells that are primarily made of lignin, which acts like glue to hold cells together. The lignin reacted with hydrogen sulphide produced by marine bacteria, accumulating sulfur in surprising amounts. Other marine bacteria chewed up the cellulose cell walls, leaving a hollow ‘house of cards’ once the ship was pulled from the water. The sulfur may have helped preserve the ship while it was still submerged.
“The amount of accumulated sulfur in the wood was indeed unexpected, and especially the formation of organosulfur compounds. We are trying to find out more precisely what the reactions are,” Sandström said. “These compounds are also of interest for understanding how sulfur accumulates in marine sediments, and eventually ends up in fossil fuels such as oil.”
Once exposed to air, the ship faces dry perils. The Mary Rose contains a great deal of iron from corroded iron bolts, nails and other ship objects. Exposed to the oxygen in air, the iron oxidizes sulfur into sulfuric acid. Studies also show that atmospheres with high, varying humidity accelerate this process.
The ship is in no immediate danger because the acid gets washed away
during conservation. A spray treatment that replaces the water in
degraded wood with waxy polyethylene glycol so the wood does not shrink
or crack as it dries out also washes out acid. However, in the Vasa, two
tons of acid has gradually built up in the 26 years after its spray
The authors suggest that using chemical treatments to remove or
stabilize the remaining iron and sulfur compounds, and reducing humidity
and oxygen access, are necessary for long-term preservation.
At the Mary Rose Trust, conservation scientists are already
investigating new treatments to prevent new acid formation in this
British treasure. They are currently using the synchrotron facilities of
the Council for the Central Laboratory of the Research Councils (CCLRC)
in the U.K. to test the efficacy of new methods. To slow down the
oxidation reaction and prevent new acid formation, wood samples from the
Mary Rose are being treated with antioxidants in combination with low-
and high-grade polyethylene glycol. Another conservation approach is to
maintain the archaeological wood in a stable climate, with a constant
temperature and a constant low humidity of 55 percent. To maintain a
stable microclimate within the wood structure, a surface coating offers
a possible solution, although the effectiveness of this approach has yet
to be tested.
“The method used in these studies—synchrotron radiation-based x-ray
absorption spectroscopy—is a particularly powerful tool to study samples
taken directly from these ships,” said SSRL Professor and Assistant
Director Britt Hedman. “It can be used directly on the samples without
any pretreatment that could change them.”
Researchers also employed an additional approach not used on the Vasa—imaging
the wood samples with a very small x-ray beam to map where the chemical
species were located.
“This leads to a better level of understanding,” Hedman said. “We see
this as an increasingly important tool for many areas of archaeometry.”
Conservationist Jones agrees. “This ongoing research is an important
step forward in devising improvements to the current Mary Rose hull
treatment programme,” he said.
Along with the hull, some 19,000 artifacts were recovered after being
underwater for 437 years. Certain remaining sections of the bow and
anchor of the once-mighty Tudor warship will be raised to the surface on
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