Roman Seawater Concrete Holds the Secret to Cutting Carbon Emissions

Berkeley Lab scientists and their colleagues have discovered the properties that made ancient Roman concrete sustainable and durable

The chemical secrets of a concrete Roman breakwater that has spent the last 2,000 years submerged in the Mediterranean Sea have been uncovered by an international team of researchers led by Paulo Monteiro of the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), a professor of civil and environmental engineering at the University of California, Berkeley.

Analysis of samples provided by team member Marie Jackson pinpointed why the best Roman concrete was superior to most modern concrete in durability, why its manufacture was less environmentally damaging – and how these improvements could be adopted in the modern world.

“It’s not that modern concrete isn’t good – it’s so good we use 19 billion tons of it a year,” says Monteiro. “The problem is that manufacturing Portland cement accounts for seven percent of the carbon dioxide that industry puts into the air.”

Portland cement is the source of the “glue” that holds most modern concrete together. But making it releases carbon from burning fuel, needed to heat a mix of limestone and clays to 1,450 degrees Celsius (2,642 degrees Fahrenheit) – and from the heated limestone (calcium carbonate) itself. Monteiro’s team found that the Romans, by contrast, used much less lime and made it from limestone baked at 900? C (1,652? F) or lower, requiring far less fuel than Portland cement.

Cutting greenhouse gas emissions is one powerful incentive for finding a better way to provide the concrete the world needs; another is the need for stronger, longer-lasting buildings, bridges, and other structures.

“In the middle 20th century, concrete structures were designed to last 50 years, and a lot of them are on borrowed time,” Monteiro says. “Now we design buildings to last 100 to 120 years.” Yet Roman harbor installations have survived 2,000 years of chemical attack and wave action underwater.

How the Romans did it

The Romans made concrete by mixing lime and volcanic rock. For underwater structures, lime and volcanic ash were mixed to form mortar, and this mortar and volcanic tuff were packed into wooden forms. The seawater instantly triggered a hot chemical reaction. The lime was hydrated – incorporating water molecules into its structure – and reacted with the ash to cement the whole mixture together.

Descriptions of volcanic ash have survived from ancient times. First Vitruvius, an engineer for the Emperor Augustus, and later Pliny the Elder recorded that the best maritime concrete was made with ash from volcanic regions of the Gulf of Naples (Pliny died in the eruption of Mt. Vesuvius that buried Pompeii), especially from sites near today’s seaside town of Pozzuoli. Ash with similar mineral characteristics, called pozzolan, is found in many parts of the world.

Using beamlines 5.3.2.1, 5.3.2.2, 12.2.2 and 12.3.2 at Berkeley Lab’s Advanced Light Source (ALS), along with other experimental facilities at UC Berkeley, the King Abdullah University of Science and Technology in Saudi Arabia, and the BESSY synchrotron in Germany, Monteiro and his colleagues investigated maritime concrete from Pozzuoli Bay. They found that Roman concrete differs from the modern kind in several essential ways.

One is the kind of glue that binds the concrete’s components together. In concrete made with Portland cement this is a compound of calcium, silicates, and hydrates (C-S-H). Roman concrete produces a significantly different compound, with added aluminum and less silicon. The resulting calcium-aluminum-silicate-hydrate (C-A-S-H) is an exceptionally stable binder.

At ALS beamlines 5.3.2.1 and 5.3.2.2, x-ray spectroscopy showed that the specific way the aluminum substitutes for silicon in the C-A-S-H may be the key to the cohesion and stability of the seawater concrete.

Another striking contribution of the Monteiro team concerns the hydration products in concrete. In theory, C-S-H in concrete made with Portland cement resembles a combination of naturally occurring layered minerals, called tobermorite and jennite. Unfortunately these ideal crystalline structures are nowhere to be found in conventional modern concrete.

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