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Water Flows Across a Level SurfaceAuthor: Nancy McGuirePublished: 31 August 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Langmuir/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesNews: New Insights into Surface Tension of WaterNews: Walking on WaterNews: Lotus Effect at High PressuresNews: Sea-Level Rise Connected to Groundwater Use

Microfluidic devices use chemical gradients to drive small amounts of liquid. Physical gradients can drive liquidsas well: Stephanie Hiltl and Alexander Böker, Fraunhofer Institute for Applied Polymer Research, Potsdam-Golm,Germany, propelled water droplets across surfaces using interfacial energy imbalances between the droplets'leading and trailing edges.

The researchers made substrates with sine wave-shaped wrinkles by coating stretched poly(dimethylsiloxane) withrigid silica and allowing the strain to relax. Various preparation methods created wrinkles of constant size or gradientwrinkle patterns. Water droplets remained stationary on substrates that were flat or that had uniform wrinkles.Contact angles were greater on the wrinkled substrates, indicating less wetting.

Droplets jumped sideways as they made contact with wrinkle-gradient substrates, and then moved toward thesmaller wrinkles. Contact angles were intermediate between those for the flat and the uniform-wrinkle substrates,but each droplet had a larger contact angle on the leading edge than on the trailing edge. As a droplet moved, itstwo contact angles decreased and became closer in size. The droplet's leading edge pinned to the substrate, freeditself, and pinned again. The trailing edge moved continuously.

The researchers foresee using wrinkled substrates for microfluidic devices, sensors, or transport systems forreagents or drugs.

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Polymer Cylinders Are Almost Two-FacedAuthor: Nancy McGuirePublished: 30 August 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Langmuir/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesMagazine: F. Svec: It's A Lot Of Plastic That Has To Be Produced!Magazine: Shedding Light on a Molecular EngineNews: Janus NanotubesMagazine: Assembly of Gold Nanoparticles

Janus particles, whose opposing faces have different chemical properties, can stabilize emulsions, serve ascatalysts and nanomotors, and provide binary capabilities in optical applications. Recently, Janus films have beenfabricated, but making Janus cylinders has proven to be more difficult.

Olivier Colombani, LUNAM Université, Université du Maine, Le Mans, France, and colleagues have beenfunctionalizing urea compounds with polymeric side chains to form self-assembled "bottle brush" structures withhydrogen-bonded urea cores. They predicted that this could be a simple method of making Janus cylinders. To testtheir prediction, they used two incompatible polymers, polystyrene and poly(isobutylene), for the side chains. Theyprepared their molecular assemblies in cyclohexane at 20 °C.

This method produced "patchy" bottle brushes, which contain partially segregated polystyrene and poly(isobutylene)regions. The researchers predict that increasing the length of the polymer arms or using more strongly incompatiblepolymers could increase the degree of segregation and produce a true Janus cylinder with two distinct sides.

Patchy Supramolecular Bottle-Brushes Formed by Solution Self-Assembly of Bis(urea)s and Tris(urea)s Decoratedby Two Incompatible Polymer Arms,Sylvain Catrouillet, Laurent Bouteiller, Olivier Boyron, Cédric Lorthioir, Erwan Nicol, Sandrine Pensec, OlivierColombani,

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Old Bricks Glaze New TilesAuthor: Nancy McGuirePublished: 24 August 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Ceramics International/Elsevier

Related ArticlesMagazine: Crystalline 2D DNA Origami ArraysNews: Making Emoticons with DNANews: Bio-Based LEGO BricksNews: Fundamental Assumptions for DNA Self-Assembly

Construction activities have increased worldwide over the past century. This is both a sign of good economic health and atremendous generator of waste materials. Recycling and recovery rates for construction and demolition wastes range from 10 % to90 % across the EU.

In light of the European "zero waste" program, M. I. Domínguez, S. Ivanova, and colleagues, Sevilla Institute of Materials Sciences,Spain, developed a way to turn some types of waste into glassy enamels and cellular glass "foams". Their process involves vitrifyingpowders made from bricks, glazed tiles, or concrete waste mixed with MgO, SiO2, or NaOH. For wastes with a high aluminacontent, an Na2O flux helps ensure complete vitrification.

The powdered mixtures can be applied directly to tile surfaces, then fired at 1100–1200 °C. Alternatively, powders can be fired andquenched in water to form glassy solids, which are then reground into powder, applied to tiles, and fired to form a glaze. The secondmethod produces a more uniform color.

Making cellular glasses requires the addition of a foaming agent, followed by thermal treatment. These lightweight expandedglasses are fireproof and waterproof, and they are good thermal and acoustic insulators.

Recycling of construction and demolition waste generated by building infrastructure for the production of glassy materials,A. Domínguez, M.I. Domínguez, S. Ivanova, M.A. Centeno, J.A. Odriozola,Ceram. Int. 2016, 42, 15217–15223.DOI: 10.1016/j.ceramint.2016.06.157

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New Ceramic-Sintering SolutionAuthor: Nancy McGuirePublished: 15 August 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: ACS Applied Materials and Interfaces/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

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During sintering, ceramic powders are heated about halfway to their melting point to compress them into a denser solid. Thispractice is energy-intensive and it is restricted to materials that can withstand high heat.

Hanzheng Guo, Clive Randall, and colleagues, The Pennsylvania State University, University Park, USA, have developed a "coldsintering" process, which uses pressurized water to partially dissolve particle surfaces. The particles can then rearrange in a morecompact way and the gaps between them can be closed when the water evaporates [1]. They modified their process for use withBaTiO3, an important material in the electronics industry that is typically sintered at 1200–1400 °C. They maintained a high bariumion concentration in the solution phase to retard leaching of barium ions from the particle surfaces, and they added titanium ions topromote BaTiO3 precipitation.

When the team cold-sintered pre-annealed BaTiO3 pellets at room temperature, capillary forces and pressure drove water into thepore spaces and partially dissolved the particle surfaces. Next, they raised the temperature to 180 °C to evaporate some of thewater and re-precipitate ions onto the surfaces, joining the particles together. After post-annealing at 700–900 °C, the pelletsreached a relative density of about 95 %.

Hydrothermal-Assisted Cold Sintering Process: A New Guidance for Low-Temperature Ceramic Sintering,Hanzheng Guo, Jing Guo, Amanda Baker, Clive A. Randall,ACS Appl. Mater. Interfaces 2016.DOI: 10.1021/acsami.6b07481

References

[1] Protocol for Ultralow-Temperature Ceramic Sintering: An Integration of Nanotechnology and the Cold Sintering Process,Hanzheng Guo, Amanda Baker, Jing Guo, Clive A. Randall,

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3/19/2017 Semiconductors Go Wavy in the Cold :: News :: ChemistryViews

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Semiconductors Go Wavy in the ColdAuthor: Nancy McGuirePublished: 19 July 2016Copyright: Wiley­VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Inorganic Chemistry/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesMagazine: Carbon­Based Electronics in Sight?News: Two at a TimeNews: Gas Absorption into a Two­layer FilmMagazine: Solar Control Coatings for Reduced Energy ConsumptionTransition­metal pnictides (group 15 compounds) are potentially interesting electronic materials, forming superconductors,thermoelectric compounds, and layered structures. As a part of a study to identify new solid ion conductors, Tom Nilges andcolleagues, Technical University Munich, Germany, explored the isostructural Zintl phases (polyanionic compounds) NaCd4P3and NaCd4As3.

The researchers synthesized the compounds from the elements under an argon atmosphere, with CdI2 as a mineralizer.NaCd4P3 (pictured) forms platelike crystals with a metallic luster. This phosphide is a new member of the RbCdAs3 structurefamily, and it undergoes a reversible rhombohedral­to­monoclinic phase transition at 260 K, driven by secondary attractiveinteractions within the Cd­P polyanionic substructure. The low­temperature (monoclinic) polymorph has an incommensuratemodulated structure, which was more pronounced for the phosphide than for the arsenide.

The thermoelectric properties of the phosphide are typical of an n­type semiconductor, while the arsenide is a semimetal.Quantum chemical calculations determined a band gap of 1.05 eV for the β phase of NaCd4P3 and 0.43 eV for β­NaCd4As3.

Polymorphism in Zintl Phases ACd4Pn3: Modulated Structures of NaCd4Pn3 with Pn = P, As,Carolin Grotz, Maximilian Baumgartner, Katharina M. Freitag, Franziska Baumer, Tom Nilges,Inorg. Chem. 2016.DOI: 10.1021/acs.inorgchem.6b01233

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A Gap Between Band Gap ValuesAuthor: Nancy McGuirePublished: 18 July 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Inorganic Chemistry/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesMagazine: As and Sb Monolayers as 2D SemiconductorsNews: Molybdenum Disulfide Switches Under PressureMagazine: Carbon-Based Electronics in Sight?News: Bismuth Phosphors in Every Color

Density functional theory (DFT) is a tried and true method for exploring the electronic properties of materials, but venturing intonew territory can produce unexpected results. James Ibers, Northwest University, Evanston, IL, USA, and colleagues found this outwhen they characterized BaUSe3 during an exploration of the Ba/U/Se ternary system.

The BaUSe3 crystal structure (pictured) is related to the perovskite structure. Its calculated activation energy (0.12 eV), based onresistivity measurements, is typical of a narrow band gap semiconductor, consistent with the black color of the compound. TheUV-vis spectrum confirmed that BaUSe3 has no optical band gap greater than 1 eV. However, DFT calculations based on the crystalstructure predict a band gap of 2.5 eV, characteristic of a relatively large band gap semiconductor.

The structural results were obtained at 100 K, and the resistivity measurements and UV-vis spectrum were obtained at 298 K, butBaUSe3 has no phase transition between these two temperatures. This large discrepancy in band gap values was not seen in manyprevious studies of similar compounds. The researchers suggest a shortcoming in the DFT calculations when dealing with thisactinide compound.

Synthesis, Crystal Structure, Theoretical, and Resistivity Study of BaUSe3,Jai Prakash, Maria S. Tarasenko, Adel Mesbah, Sébastien Lebègue, Christos D. Malliakas, James A. Ibers,Inorg. Chem. 2016.DOI: 10.1021/acs.inorgchem.6b01202

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3/19/2017 Anatomy of an Explosion :: News :: ChemistryViews

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Anatomy of an ExplosionAuthor: Nancy McGuirePublished: 01 July 2016Copyright: Wiley­VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Analytical Chemistry/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesNews: Concentrating on ExplosivesNews: Explosive ChemometricsNews: Explosives Detection GelsMagazine: Far Too Sensitive ExplosivesMany analytical techniques can identify explosive materials before they are detonated, and these efforts are vital inpreventing terrorist acts. After an explosion, however, residues are dispersed over a large area and mixed with other particlesfrom the surroundings, complicating identification.

Félix Zapata and Carmen García­Ruiz, University of Alcalá, Madrid, Spain, used confocal Raman microscopy to identifyexplosion residues. They tested their method using ten explosives that are commonly used in improvised explosive devices.

Before detonation, homogeneous organic explosives (TNT, RDX, PETN, TATP, and HMTD) all have characteristic Ramanspectra. For heterogeneous inorganic/organic mixtures (black powder, dynamite, chloratite, ANFO, and ammonal), the Ramanspectrum varies across the sample, and the spectra have fewer peaks.

After detonation, the Raman technique rapidly and selectively identified particles of the heterogeneous explosives as small as10 μm in diameter. Because some particles of the combustible compounds were not in contact with the oxidizer, they survivedthe blast. No surviving homogeneous organic explosive particles could be detected, because the combustible species and theoxidizer are contained within a single compound.

Abbreviations

TNT: 2,4,6­trinitrotolueneRDX: Research Department explosivePETN: pentaerythritol tetranitrateTATP: triacetone triperoxideHMTD: hexamethylene triperoxide diamineANFO: ammonium nitrate/fuel oil

3/19/2017 A More Fundamental Kilogram :: News :: ChemistryViews

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A More Fundamental KilogramAuthor: Nancy McGuirePublished: 30 June 2016Copyright: Wiley­VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Analytical Chemistry/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesNews: Making Kilograms of Ethenesulfonyl FluorideJournal: Journal of Polymer Science Part A: Polymer ChemistryJournal: International Journal of Cosmetic ScienceMagazine: Fundamental Research Needs Excellent Scientists and its Own SpaceThe kilogram (kg), the only remaining SI unit based on a physical object, is set to relinquish its unique status in 2018.The new kg definition will rely on mass measurements based on Planck's constant and Avogadro's constant.

A 2015 study achieved the required precision (2.0 · 10–8 relative standard uncertainty) using X­ray crystal density to count thesilicon atoms in a one­kilogram 28Si­enriched single crystal sphere [1]. The isotopic enrichment reduced background noiseproduced by 30Si and 31Si present in natural silicon.

Verifying these results required an extremely precise evaluation of the ultratrace impurities present in the silicon sphere.Giancarlo D’Agostino, Istituto Nazionale di Ricerca Metrologica, Torino, Italy, and colleagues examined two 5.2­gram samplesfrom the sphere using instrumental neutron activation analysis, collecting their data at research reactor neutron sources inItaly and Australia.

The team quantified the concentrations of 12 elements and determined the detection limits of another 54 elements. Theydetermined that the difference between the mass of an idealized one­kilogram silicon sphere and the actual sphere is 1.154μg.

Purity of 28Si­Enriched Silicon Material Used for the Determination of the Avogadro Constant,Giancarlo D’Agostino, Marco Di Luzio, Giovanni Mana, Massimo Oddone, John W. Bennett, Attila Stopic,Anal. Chem. 2016.DOI: 10.1021/acs.analchem.6b01537

References

A Wireless Network Based on LightAuthor: Nancy McGuirePublished: 21 June 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: ACS Photonics/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesNews: International Consortium Develops Dye-sensitized Solar CellsMagazine: Bow Down to the LightNews: Miniaturized Power Modules for Aircraft MaintenanceMagazine: More Transparency

Visible light communication is a promising solution to the ever-increasing demand for data capacity in wirelesscommunications. It provides greater bandwidth and a less crowded spectrum than do radio frequency and microwave technologies.However, the phosphors currently used with LED light sources cannot provide sufficient bandwidth for telecommunications signalmodulation.

Boon Ooi, Osman Bakr, and colleagues, KAUST, Thuwal, Saudi Arabia, developed a phosphor system that converts blue GaN laserdiode light to white light. Green-emitting CsPbBr3 perovskite nanocrystal phosphors, coupled with a conventional red-emitting nitridephosphor, produce white light with a modulation bandwidth of 491 MHz. This is about 40 times greater than for conventionalphosphors, corresponding to a data transfer rate of as much as 2 gigabits/second.

One advantage of CsPbBr3 is its relatively short phospholuminescent lifetime, which enables faster optical data transfer rates. Likeother lead halide perovskites, CsPbBr3 offers long-range charge transport, tunable emission in the visible spectrum, low cost, andease of processability. According to the researchers, the next step is to develop encapsulation and packaging processes to ensurethat lighting devices using this technology can operate reliably.

Perovskite Nanocrystals as a Color Converter for Visible Light Communication,Ibrahim Dursun, Chao Shen, Manas R. Parida, Jun Pan, Smritakshi P. Sarmah, Davide Priante, Noktan Alyami, Jiakai Liu, MakhsudI. Saidaminov, Mohd S. Alias, Ahmed L. Abdelhady, Tien Khee Ng, Omar F. Mohammed, Boon S. Ooi, Osman M. Bakr,ACS Photonics 2016.DOI: 10.1021/acsphotonics.6b00187

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Raspberry LogicAuthor: Nancy McGuirePublished: 20 June 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaASource / Publisher: ACS Applied Materials and Interfaces/American Chemical SocietyAssociated Societies: American Chemical Society (ACS), USA

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Micromotors, particles that move in response to chemical or electrical stimuli, have been used to clean up pollutants,transport other particles, or act as sensing devices.

Bin Dong and colleagues, Soochow University, Jiangsu, China, created micromotors that act as programmable logic circuits. The13-micron particles contain the enzyme catalase and conductive polypyrrole nanoparticles suspended in gelatin and paraffin. Thepolypyrrole nanoparticles form bumpy protrusions that give the micromotors a raspberry shape. The catalase componentdecomposes hydrogen peroxide to form oxygen bubbles, which propel the irregularly-shaped micromotors in random directionsthrough an aqueous solution.

Catalase is most active at pH 7. It can be temporarily deactivated with ammonia and then restarted with HCl gas. Near-IR light canbe used to steer the nanomotors, triggering a photothermal response from the polypyrrole nanoparticles and driving themicromotors away from the light source. Ammonia deprotonates the polypyrrole, dampening the photothermal effect, and treatmentwith HCl reactivates the nanoparticles. Various combinations of hydrogen peroxide, light, and ammonia start and stop themicromotors, creating the AND, OR, and NOT logic operations.

Reprogrammable Logic Gate and Logic Circuit Based on Multistimuli-Responsive Raspberry-like Micromotors,Lina Zhang, Hui Zhang, Mei Liu, Bin Dong,ACS Appl. Mater. Interfaces 2016.DOI: 10.1021/acsami.6b04674

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Sparkling Wine: Timing is EverythingAuthor: Nancy McGuirePublished: 17 June 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaASource / Publisher: Journal of Agricultural and Food Chemistry/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

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Sparkling wines represent a small but lucrative part of the wine market. Red sparkling wines are emerging as a result of recentefforts to diversify the available types of sparkling wine. Preserving a fresh, light taste during the secondary fermentation processrequires that grapes be harvested earlier for sparkling wines than for still wines. Complex carbohydrates, which evolve during graperipening, affect the fermentation and sensory properties of the wine. However, little is known about how they develop during themaking of red sparkling wines.

Leticia MartÃnez-Lapuente, Instituto de Ciencias de la Vid y del Vino, Logroño, Spain, and colleagues studied two batches of redsparkling wine made from Tempranillo grapes, harvested ten days apart, from a single vineyard. Riper grapes produced wines withpolysaccharides and oligosaccharides distributed more broadly over a range of molecular weights than did less mature grapes. Allof the wines had similar oligosaccharide concentrations, but oligosaccharides from riper grapes were more soluble and stable.Wines from riper grapes had higher mannose concentrations, possibly because of their higher higher alcohol content, but after 6months of aging, these levels fell significantly, possibly because of colloid formation and precipitation.

The results suggest a grape ripening influence on sparkling wine carbohydrate concentration, composition, and structure.

Influence of Grape Maturity on Complex Carbohydrate Composition of Red Sparkling Wines,Leticia Martínez-Lapuente, Rafael Apolinar-Valiente, Zenaida Guadalupe, Belén Ayestarán, Silvia Pérez-Magariño, PascaleWilliams, Thierry Doco,J. Agric. Food Chem. 2016.DOI: 10.1021/acs.jafc.6b00207

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A Sea Full of Plastic ParticlesAuthor: Nancy McGuirePublished: 04 June 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Environmental Science & Technology/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesNews: Ubiquitary Plastic PollutionNews: First Study of Microplastics in RiversNews: Increased Deep-sea PollutionNews: Plastic in Deep Seas

According to a recent estimate, 4.8–12.7 million metric tons of plastic waste end up in the ocean each year, and this wastebreaks into fragments with sizes of 0.5–5 mm. Little is known about the pathways and fate of these plastic fragments.

Alexandra ter Halle, Université Paul Sabatier, Toulouse, France, and colleagues analyzed 1275 plastic debris particles (5.8 g totalmass) from the sea surface in the North Atlantic subtropical gyre (a system of rotating ocean currents). They found that thin flatfragments float with one face preferentially exposed to the sun. This face typically cracks more, but fewer organisms grow on it.Cubic particles, which roll in the water, exhibit the same characteristics on all faces, with fewer cracks and fewer attachedorganisms.

In 2012, Europeans used 1.5 times more polyethylene (PE) than polypropylene (PP), but the researchers found nine times as manyPE particles as PP particles in the ocean. This could reflect differences in duration of use for various items, in where these itemstend to be discarded, and in rates of photodegradation and fragmentation. The team notes a conspicuous lack of ultra-small plasticparticles, and they call for new research to investigate what happens to particles smaller than 300 microns in the ocean.

Understanding the Fragmentation Pattern of Marine Plastic Debris,Alexandra ter Halle, Lucie Ladirat, Xavier Gendre, Dominique Goudouneche, Claire Pusineri, Corinne Routaboul, ChristopheTenailleau, Benjamin Duployer, Emile Perez,Environ. Sci. Technol. 2016.DOI: 10.1021/acs.est.6b00594

Also of Interest

Plastic in Deep Seas,Veronika Belusa,

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Lead in Your LipstickAuthor: Nancy McGuirePublished: 01 June 2016Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimSource / Publisher: Environmental Science & Technology/ACS PublicationsAssociated Societies: American Chemical Society (ACS), USA

Related ArticlesNews: Lipstick at Crime ScenesEducation: Talking in Poster Sessions: Breaking the Ice (1)Education: Tips for Your Poster: Designing Your Poster (3)Education: Tips for Your Poster: Presenting You and Your Poster (4)

By some estimates, a woman may ingest about 1.8 kg of lipstick over the course of a lifetime, along with the lead-basedcoloring agents these products contain. To see how much this adds up to, Hong-Bo Li, Lena Q. Ma, Nanjing University, China, andcolleagues measured lead quantities and bioavailabilities in 75 lipsticks and 18 lip glosses, as well as the concentrations of six othermetals (Co, Cd, As, Ni, Cr, Zn).

Lead concentrations ranged from 0.2 to 10,185 mg/kg and averaged 497 mg/kg. These values were significantly higher than thosefor any of the other metals. Orange and pink shades contained more lead (presumably as PbCrO4) than brown, red, or purple ones.More expensive products contained less lead, and European and American products contained less lead than Iranian and Saudiproducts, which in some cases contained several grams of lead per kg product.

The team estimated a daily lead intake between 0.04 and 1.5 µg/kg body weight from lipstick or lip gloss when bioavailability wastaken into account. For some products, lip product users with a particularly high rate of ingestion (highest 5 %) could take upamounts of 5.31 µg lead/kg body weight daily, which exceeds the provisional tolerable daily intake level of 3.5 µg/kg body weight.

The researchers suggest that lead speciation studies should be performed to assess the effects of various lead compounds onbioavailability, especially for five of the tested products that had unusually large bioavailability results. They also recommend similarstudies on chromium concentrations and bioavailability.

Lead Relative Bioavailability in Lip Products and Their Potential Health Risk to Women,Di Zhao, Jie Li, Chao Li, Albert L. Juhasz, Kirk G. Scheckel, Jun Luo, Hong-Bo Li, Lena Q. Ma,Environ. Sci. Technol. 2016.DOI: 10.1021/acs.est.6b01425

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