Current events involving politics, political office holders, political candidates, world events, local events, crime and other public affairs issues are discussed. Business news items as well as science and technology issues may appear.
On Oct. 1, Lisa Buckley's security management firm is due to bill thousands of dollars in new business to Uncle Sam. But if thegovernment shut downs at 12:01 a.m. Tuesday, those invoices could remain unpaid indefinitely.
Silvio Berlusconi has plunged Italy into another political crisis. It's a wake-up call for Europe and a reminder that, despite what the recent German election campaign suggested, the euro crisis is by no means over yet.
Thousands of economic refugees flood into Berlin every year, including many Roma. Some end up homeless, many are insulted or spat upon. Now a new program aims to help them find jobs and apartments -- and begin a new life.
Prosecutors claim 93-year-old former Auschwitz worker Hans Lipschis is complicit in the murder of thousands of people. The charges raise questions about how to interpret guilt in the Holocaust, as well as why the German justice system waited so long to pursue such cases.
It's quickly becoming clear how hard it's going to be for Angela Merkel to form a new government. The SPD wants the Finance Ministry and will ballot its members on any deal. In the end, though, they're likely to reach an agreement, say media commentators.
They murder, rob and kidnap, just like their male comrades. Some women fight for rebel groups in Congo against their will, while others are driven by desperation. Photographer Francesca Tosarelli documented their dangerous lives.
The European Central Bank wants to impose rigid tests on financial companies in the euro zone before it assumes its new supervisory role. But even before the tests are set to begin, the ECB is already tangling with policymakers.
Austrians voted on Sunday to re-elect their current coalition government. But the country's two largest parties saw their worst nationwide election results since World War II while the right-wing populists made substantial gains.
For some 200 years, Oktoberfest has been all about copious amounts of beer and meat. But, this year, organizers are breaking with tradition and reaching out to visitors with dietary restrictions by offering vegan dishes and even vegan wine.
Septegenarian Ziad Nouri spent more than three months in the hands of jihadist kidnappers in Syria. His story highlights the problem of abductions in a country fractured by civil war and upstart foreign Islamists without a plan.
Foreign Islamists coming into Syria have been gathering in the relatively quiet north. But many of them are finding transit towns -- with good food, video games and smoking -- preferable to the front. When they do end up fighting, it's often with each other.
For decades, it's been common knowledge that dolphins are among the world's smartest species. Now some researchers -- and a new book -- argue the supposed underwater geniuses aren't so special after all.
A grand coalition has ruled Austria for almost seven years and most of the postwar period. But rising support for upstart and populist parties could disrupt that trend after Sunday's parliamentary elections.
When she was 13, Samantha Geimer was raped by Roman Polanski at Jack Nicholson's home in Los Angeles. She has written a new book about that night in 1977 and its aftermath. In an interview with SPIEGEL, she tells why she still doesn't hate the director.
Chancellor Merkel's conservatives unequivocally rejected tax increases in the recent election campaign. But now that they need to find a coalition partner among left-leaning parties, their tone seems to be changing.
A total of 32 people died when the Costa Concordia capsized off the Italian island of Giglio last January, but only 30 bodies were recovered at the time. Italian authorities have now recovered human remains after the ship was pulled upright.
"Forest Boy Ray" intrigued Europe when he turned up in Berlin pretending to have lived in the woods for years. When it all turned out to be lies, he was charged with fraud. But a court has now decided to drop the charges if he completes community service.
As Germany's Finance Minister, Wolfgang Schäuble is one of Europe's most influential politicians -- and one of its most hated. Many hold his austerity policies responsible for mass poverty and unemployment in the south. How does he know his decisions are right?
Until now, train passengers in Europe delayed by bad weather or worker strikes had no recourse to compensation. That has changed, however, with a court ruling on Thursday requiring railway companies to refund part of the ticket cost in such situations.
Faced with a computer glitch that delayed unemployment checks to more than 80,000 residents, the state of California will pay out all backlogged jobless claims, regardless of whether they are valid or not.
Parliamentarians with foreign roots were considered exotic in Germany for a long time, but that has changed. Candidates with Turkish heritage now represent a new force in the country's political landscape.
Germany's euroskeptic Alternative for Germany party came tantalizingly close to the threshold needed for parliamentary representation in Sunday's election. But it failed. Now members are worried that the young party could unravel.
The Social Democrats hate the idea of a coalition with Angela Merkel, but media commentators say the party will probably have to accept one -- and could even benefit if it extracts the right price. A Merkel coalition with the Greens is possible, but unlikely.
A sigh of relief can be heard around the Continent, where many European countries states are hopeful that a left-leaning German coalition partner could steer Angela Merkel toward a gentler course and less austerity in managing the euro crisis.
Germany's influence in Europe is at its highest in decades, and leaders around the world watched the federal election closely. Now embarking on her third term, Chancellor Angela Merkel remains a uniting figure at home and a polarizing figure abroad.
Despite years of warnings and millions of dollars lost, people are still falling for one of the most common scams on the books: a fraudster contacts you, saying you've won a lottery or sweepstakes -- you just need to send in a small sum of money to collect your huge cash prize.
As one professional roller girl once declared, "A pretty face and cleavage is all you really need!"
Despite its best efforts, the science and technology sector is failing to attract girls, potentially undermining Germany's strength as a global export power. Now some are getting creative, launching preschool initiatives and even a new soap opera.
Imhan K., a Turkish woman living in Germany, had her welfare benefits slashed after her husband refused to let her take German courses. Now a court must decide whether immigrants can be forced to learn the language and adopt Western mores.
Germany's Green Party faces a shake-up after its poor performance in Sunday's election, with lead candidate Jürgen Trittin the latest to step down. Now former head Joschka Fischer is taking the party's leadership to task, as the finger pointing begins in earnest.
Chancellor Merkel is likely heading towards a coalition with the Social Democrats. SPD leaders have begun making concrete demands for changes to her policies on Europe. European Parliament President Schulz wants quick action.
Gen. Salim Idriss is head of the Free Syrian Army. In a SPIEGEL interview, he discusses why the chemical weapons deal with Assad is a ruse, why the West worries too much about Islamic extremists and how he coordinates his forces via Skype.
Angela Merkel can now start looking for a coalition partner, but it will not be simple. The SPD and the Greens are both skittish about an alliance with her CDU -- and have good reason to be. Difficult negotiations lie ahead.
Angela Merkel clearly won Sunday's German election, but she will need a coalition partner. Many in Europe are hoping an alliance with the center-left Social Democrats would mean a change in the chancellor's harsh austerity policies. Those hopes may be dashed.
While the West is trying to extricate itself from the war zone in Afghanistan as quickly as possible, old warlords like Ismail Khan are preparing for a post-withdrawal period that many anticipate will be violent.
Despite falling short of the 5 percent hurdle required to enter parliament, the euroskeptic Alternative for Germany party performed surprisingly well in the German election. Experts say the party shouldn't be underestimated.
When she took over the Christian Democrats 13 years ago, few thought Angela Merkel would last long. But after her resounding victory on Sunday, it is now clear that she has become so much more than just Germany's political leader.
The biggest losers of the German election are the pro-business Free Democrats, who failed to make it into parliament. After decades of playing kingmaker, its spectacular defeat marks a seismic shift in Germany's political landscape.
It hardly gets any more exciting, more enthralling or more spectacular. This 2013 German election represents a watershed. The chancellor has triumphed, and her coalition partners the pro-business Free Democrats are shattered. Germany is well and truly Angela Merkel country.
Chancellor Merkel has run a bland re-election campaign. But that is exactly what voters were looking for. There are many reasons why she will win a third term on Sunday, but the primary one is her deep understanding of what the German electorate wants.
The Rosia Montana mine in Romania is currently one of Europe's most controversial projects. Plans by Bucharest to push through approval for the large-scale mining that would eliminate an entire town have sparked mass protests.
Sierra Hellstrom, Nature High Summer Camp director, explains to student about the core sample taken from an aspen tree.
In a few short years, high school students at Nature High Summer Camp on the Manti-LaSal National Forest in Utah may become newly minted natural resource professionals who make a difference in the world of natural resources.
The 30 high-school students from Utah met as strangers on a Monday morning, but left Saturday as good friends who connected with nature in a way they had never before experienced.
“It’s amazing to see the changes in the students over the course of a week,” said Sierra Hellstrom, camp director who works in the U.S. Forest Service’s Intermountain Region. “They arrive shy and scared, with little knowledge of public land management. They leave enlightened and a very tight-knit group, and have a hard time saying goodbye to one another.”
The 22-year-old camp, a partnership with several government agencies, introduces students to “a day in the life” of a natural resource professional to learn about the complexities of public land management.
They work with silviculturists – or forester – to learn how to core trees to gather information on the age of stands (grouping of trees), health of trees, and other vital information.
Working with biologists, students learn about aquatic insects and how their presence – or absence – can reveal water quality. Students don waders and spend a morning catching samples in nets to identify and then interpret what they have discovered and how that relates to the entire watershed.
Hanna Gold, a senior from Layton, Utah, examining her findings while using a D-net to collect specimens of aquatic insects.
A soil scientist helps the students get literally dirty by digging a plot of soil so they can study the layers, the health of the surrounding area and other variables that affect how the soil is compacted.
A hydrologist and students carrying high-tech instruments wade into the water to test stream flow, temperature and other factors to determine spring run-off numbers and how they will affect the water supply throughout the summer.
Then they hike through the forest with an entomologist to learn that a very small insect – a bark beetle – in large numbers and under the right conditions can kill millions of trees. The students collect insect samples then return to camp to study them.
The students, by working in the field with professionals, also learn how science contributes to public policy and the eventual decisions that shape the public’s use of 193 million acres of national forests and grasslands.
“We cram a lot into a small period of time,” Hellstrom said. “But each segment is important. We can only hope that during that week we planted a seed in the minds of these young people who may see natural resources as a viable career choice. At the very least, we hope that they grow into adults who understand the connection between the natural world and our everyday lives.”
The success of camp is also measured by how many students eventually find internships, summer work or volunteer opportunities with natural resource agencies.
Perhaps the success of the program can best be summed up with a written critique from a camper: “I have a new outlook on life and people in general. We really can make a difference.”
Eneida Rosas, a senior from Logan, Utah, learns how to take a tree core sample with an increment borer.
After some initial digs, a Dutch filmmaker believes he may have found the site of buried Nazi treasure long rumored to exist. He was led to the Bavarian town of Mittenwald after cracking a code believed to be hidden in a music score.
The hacking attack by Britain's GCHQ intelligence service on Belgian telecoms provider Belgacom has angered politicians in the country. Belgium plays host to the EU's top institutions as well as NATO, and Prime Minister Elio di Rupo is considering diplomatic retaliation.
A new study shows that Germany contributes less per person to the permanent euro bailout fund than residents of several other countries in the European Union. Luxembourg, Holland and Ireland are among the nations paying more per capita.
With the help of intellectuals and celebrities, not voting has recently become de rigueur in Germany. But declining voter turnout harms democratic legitimacy, bolsters the power of those who prompted discontent and could sway Sunday's election.
Millions of Indian children work as slaves in factories, brothels or in the homes of families. Out of poverty and desperation, parents sell their daughters, and human traffickers wait at train stations for runaways and scour for orphans in monsoon-ravaged villages.
A cyber attack on Belgacom raised considerable attention last week. Documents leaked by Edward Snowden and seen by SPIEGEL indicate that Britain's GCHQ intelligence agency was responsible for the attack.
The alleged murder of a leftist rapper by a neo-Nazi has shocked Greece, where thousands have taken to the streets to protest the rise of the far-right Golden Dawn party. Athens says it is determined to take action.
The Pinchot legacy continues for future generations with programs offered at Grey Towers. Credit: US Forest Service, Grey Towers NHS
A beautiful, blue stone mansion with its slate roof and turrets, known as Grey Towers, in Milford, Pa. has been a sanctuary for visitors from around the world to learn about conservation and natural resources.
On Sept. 19-22, the Forest Service, the Pinchot Institute and the Grey Towers Heritage Association will celebrate Grey Towers’ golden anniversary with public and private events, receptions, lectures, honored guest speakers, public visitation and family programs. This commemoration is an opportunity for the Forest Service, and its partners and collaborators to celebrate Pinchot’s legacy and highlight the many contributions he made to the Forest Service and beyond. What better way to honor the conservation legacy of the father of American conservation than by offering the Pinchot home as a public center for tours, meetings, study and research.
President Kennedy gets approval from audience and dignitaries at Grey Towers dedication ceremonies of Pinchot Institute for Conservation Studies. Note: Others on stage -- Secretary of Agriculture Orville Freeman, Chief of the Forest Service, Edward P. Cliff, Pres of the Conservation Foundation Samuel Ordway, and Governor of PA, William Scranton. Credit: US Forest Service, Grey Towers NHS
The historical Grey Towers was first completed in 1886. Eight decades later, the site was designated as a National Historic Landmark. In 1980, more than $16 million in federal, state, and private funds were raised to complete a comprehensive restoration of the historic features and the renovation of the building and estate for “adaptive re-use” as a world-class conference center. The Pinchot Institute for Conservation Studies, which was established on this site, has served as a center for today’s most challenging environmental issues.
President Kennedy with Dr. and Mrs. Pinchot at the Finger Bowl where historic conversations were held. Credit: US Forest Service, Grey Towers NHS
The Forest Service, along with its partners, is carrying out Pinchot’s legacy of “practical idealism,” and his philosophy that in order to be effective, natural resource conservation must be not only ecologically sound, but economically viable and socially responsible. To this day, Pinchot’s philosophy of providing “the greatest good for the greatest number in the long run” is the driving principle behind the Forest Service’s approach to natural resources management.
Gifford Pinchot, first chief of the US Forest Service and two-term governor of Pennsylvania. Credit: US Forest Service, Grey Towers NHS
A new academic year is here for millions of students and teachers across the country, and in spirit of the many back to school nights and open houses taking place, I’m encouraging you to explore USDA’s International Year of Statistics Virtual Open House.
The International Year of Statistics, sponsored by more than 2,000 organizations – including the USDA – is a worldwide event to help teach everyone about the powerful and far-reaching effects of statistics. When people hear the word “statistics,” they often think of sports statistics or the course they took and struggled to pass. While you can think of statistics in these terms, there is more to the relationship between you and statistics than you may imagine.
For agriculture, did you ever wonder about where your food is raised, how it’s produced, and by whom? How this information impacts future food prices and availability? About weather patterns and climate change and the effects they have on crops, livestock and America’s farm land? These questions and many more can be answered with statistics that are produced by USDA.
Statistics are rewarding to us not only as statisticians, economists and researchers, but also as students, teachers, parents and consumers. They arm us with the knowledge to contribute to the wellbeing of the entire human race – the people living with us at home, to our neighbors in nearby communities, to strangers we’ve never met around the globe.
Because of agricultural statistics we can make informed buying decisions for our families, we can impact societal change by supporting U.S. farm and rural policy, and we can make strides for the future by encouraging young minds to explore careers in statistics, mathematics and science.
Amber Waves presents the economics of food, farming, natural resources and rural America in lay terms via engaging features, findings, and statistics.
CropScape, a data visualization and analysis tool with satellite derived land cover images showing the annual planted crops and the ever-changing impacts on U.S. agriculture.
Food Security Information and research that is helping provide access by all people at all times to enough food for an active, healthy life.
Quick Stats 2.0, the most comprehensive tool for accessing agricultural data published by NASS that allows you to visualize, manipulate, and export exactly the information you desire, whether it is based on commodity, location, or time period.
If you have a question, you can also connect with us on Twitter by tweeting NASS (@usda_nass) and ERS (@usda_ers). Join our virtual open house today and learn how agricultural statistics enhance the work of USDA and your life – every day and in every way!
Some scammers may offer help navigating the new health insurance marketplace under Obamacare, for a fee. Others will warn that you will need a new Medicare card. And still others may say they are from the government andneed your personal information.
Russell Wire, a northwest Illinois farmer, found cover crops to be an excellent option for his operation. His cattle enjoy grazing quality forage, and his soil health is improving as well.
At age 8, Russell Wire knew he liked agriculture. That was when he raised some beef cattle for a 4-H project, eventually turning that project into a herd of 40.
This natural affinity makes sense—Wire, who lives in northwest Illinois, comes from a farm family. The 28-year-old is actually a fifth-generation farmer.
Since 2005, Wire has worked 40 acres of pastureland, and he’s grown corn on another 50 acres since 2011. Recently he decided to incorporate cover crops into his operation to provide more forage for his herd, prevent erosion and improve soil health.
Late summer 2012 was Wire’s first year planting cover crops. He opted for a mix of annual ryegrass and tillage radish. He likes the fact that he is able to do something different for a conservation solution that will sustain his operation.
Wire used a no-till drill to seed the radishes. While the right soil temperatures are important for success, 2012’s drought conditions threatened good seed germination. Luckily, a late September rain saved the day and he was able to grow a good, healthy cover crop.
At the same time, Wire allowed forage on his pastures to grow to a height of about 20 to 24 inches. This made high moisture haylage available for the herd.
Because of the pasture’s location, he uses his cropland to grow hay instead of using it for livestock grazing. He cuts the forage when it’s ready, then bales it for later use.
According to Wire, the best part about cover crops is that they improve the health of his soil. He’s also happy to see fewer weeds due to the annual ryegrass’ dense foliage.
He’s found that the radishes effectively break up soil compaction and bring valuable nutrients back to the surface for other crops to use.
Wire is pleased with the results of his new techniques. He can watch his cover crops grow, provide quality hay and feed for his cattle, and hold back erosion. And he’s a pioneer in his area.
“A lot of people are watching me to see how it works,” he says.
In August, Merkel's government admitted that Greece needs billions of euros in additional aid. Some have called for a cut to interest rates on emergency loans made to Greece. But with the rates already so low, it would be but a drop in the bucket.
More than 1,500 inner-city youth from Houston Independent School District gather over a week-long period at Jones State Forest – Children’s Forest each year to participate in the annual Exploring Houston’s Backyard. The Bosque Móvil-Forest Mobile is one tool the U.S. Forest Service’s Latino Legacy program uses to provide learning experience around Texas.
Roughly a decade ago, Tamberly Conway impulsively agreed to leave Key West, Fla., with a friend to serve as crew members on a 47-foot sailboat with a captain they barely knew. But somewhere between Key West and Guatemala, she began reevaluating her decision.
They got off the boat in Guatemala and spent the next year absorbing the Latino culture and Spanish language. She turned that unexpected experience into helping the U.S. Forest Service reach out to the Latino community. Along with her multiple degrees in natural resources, Conway connects Latinos to the natural world around them through such programs as Latino Legacy.
“These programs provide avenues for students who gradually gain a sense of empowerment,” Conway said. “They understand that it’s okay to be a leader in this arena and help their community understand the need to take care of the land and conserve what they have. I tell them, ‘You can be leaders in this area so you can improve your nation’s food sources and make sure we have enough wood, water and wildlife in the future.’”
Stationed in Texas, Conway’s first project after joining the Forest Service five years ago centered on development of the Latino Legacy program, created in large part through a More Kids in the Woods cost-share initiative and partnership funds. Latino Legacy program goals are to develop, implement and evaluate culturally appropriate conservation education programs designed for urban and rural Latino communities. It has since evolved into a hub for a number of programs focusing on diversity outreach and conservation education.
Forest Service conservation education specialist Tamberly Conway talks about how to use binoculars for wildlife viewing to members of the Chikawa-Aztec Cultural Troupe during the Wild About Wings program at Jones State Park in Texas.
The two primary outreach tools are the “Bosque Movil,” or forest mobile, a mobile information and activity station, and the “Amigos de Bosque,” or the Friends of the Forest, a semi-bilingual conservation education and community outreach team, managed by the Friends of the National Forests and Grasslands in Texas.
The Friends organization was formed to help the Forest Service make the 600,000 acres of forests and grasslands in that state more accessible to diverse audiences. Together with strong partners like the Texas A&M Forest and Stephen F. Austin State University, the program has reached at least 250,000 people, although some supporters believe the number to be more than double that amount.
“We are able to go into schools that have high populations of Latinos and engage not only the students but also educators, administrators, parents and community partners,” she said. “Our work helps create a pathway to something more. Whether these youth choose to work in natural resources or not, they have a new excitement about the outdoors, and they share that excitement with others in their communities. They are becoming our current and future conservation leaders.”
Conway’s next project, in a USFS partnership with a Project Learning Tree grass-roots program called Green Schools!, will result in a national model that will target early childhood through high school in an educational feeder pattern or “grapevine,” with a strong focus upon higher education and possible futures in natural resource careers. The Green Schools! initiative helps students improve communication, civic and leadership skills, while increasing environmental awareness. The pilot project will focus on the East End community in Houston and the Houston Independent School District, which are predominantly Latino.
A young boy, who earlier seemed disinterested, suddenly lit up during the Chikawa Aztec Cultural Troupe’s participation in the Exploring Houston’s Backyard program. Shortly after the dance performance, the young boy up to one of the performers, grabbed him and said, “This is my culture!”
Several recent controversies in Germany -- from the treatment of refugees to the obstacles faced by immigrants in the job market -- have thrown the issue of racial discrimination into the limelight. SPIEGEL spoke to 15 people of foreign descent to find out how racism affects their daily lives.
The recent severe floods in Colorado could end up costing homeowners, businesses and local governments nearly $2 billion, according to Eqecat, a firm that conducts loss estimates for the insurance industry.
Social Democratic candidate Peer Steinbrück could win Sunday's election, but he would have to partner with the Left Party in order to prevail. The leftists continue to be surprisingly strong, but their Communist roots make them an unpalatable partner.
Nurse Jennifer Witting stands beside newly installed telemedicine equipment at the Aspirus Keweenaw Hospital in Laurium, MI in June 2012. The Aspirus Health Foundation, Inc. received two Distance Learning and Telemedicine (DLT) grants through the U.S. Department of Agriculture’s (USDA) Rural Development (RD) DLT Program, that enabled Aspirus to grow their Telehealth infrastructure into communities in north-central Wisconsin and the western Upper Peninsula of Michigan. USDA photo.
This week at USDA we are celebrating National Health IT week by highlighting USDA’s ongoing efforts to expand modern health care access to rural America. Yesterday, we announced two new steps to improve health care for rural Americans – both through new investments in health infrastructure and ongoing interagency partnerships designed to better focus Federal efforts on rural health care.
USDA is expanding a partnership with HHS and the Department of Veterans Affairs, as part of our work together on the White House Rural Council, to leverage funds and other efforts that will support advanced health care technology in rural hospitals. This partnership is an extension of a successful pilot launched in five states – Illinois, Iowa, Kansas, Mississippi and Texas – to identify rural critical access hospitals in persistent poverty areas in need of advanced health care technology. For example, during the pilot phase of this partnership, the USDA Rural Development Iowa State Office, the Iowa Regional Health IT Extension Center (REC) and the Iowa State Office of Rural Health convened the first Iowa Rural Health IT Forum to expand care for Critical Access Hospitals.
Meanwhile, we are continuing to let folks know about HHS and VA health care initiatives. This has included the Department of Veterans Affairs Rural Veterans Coordination Pilot Program, to empower rural organizations in promoting high-quality health care and mental health services for our veterans. And last week, The Department of Health and Human Services Office of Rural Health Policy announced grants to build telehealth networks, delivering mental health services to rural veterans as well as funds that will recruit and train a workforce with expertise in Health IT.
We also continue to strengthen partnerships with rural communities by investing in high-quality health care infrastructure. Yesterday, USDA announced loans and grants that will help improve health care facilities – providing assistance with everything from building a new critical access hospital building, to modernizing surgical equipment and improving patient registration. These new investments complement efforts that USDA has already made, since 2009, that have expanded distance health care tools to more than 1,600 health care institutions and provided support for more than 1,000 health care facilities.
All of these efforts are helping to create a modern health care infrastructure to better serve rural Americans. At the same time, we are working together to be sure that all Americans have access to affordable health care – in particular by reminding folks across the nation that new opportunities for coverage under the Affordable Care Act will soon be available through new Health Insurance Marketplaces. Beginning in 2014, more than 7.8 million uninsured rural Americans under age 65 will have new opportunities to enroll in affordable health care.
This is critically important in rural America, where nearly one in five uninsured Americans lives and where a greater share of residents lack health insurance. A large proportion of folks in rural America will be eligible for discounted insurance coverage through their states’ Health Insurance Marketplaces, so we’ll continue helping to get the word out in rural America. The Department of Health and Human Services provides a wide range of information on the benefits of the Affordable Care Act – and how to obtain coverage if you’re not insured – on www.healthcare.gov.
Rural America faces unique barriers to health care, but together we can meet these challenges. I’m looking forward to continuing USDA’s work alongside our interagency partners that will further expand health care for rural Americans in generations to come.
This model of the guanidinium chloride salt (blue and silver) in solution shows carbon (yellow) and water (green) surrounding the cations and demonstrates cation-cation pairing.
At some point in elementary school you were shown that opposite charges attract and like charges repel. This is a universal scientific truth – except when it isn’t. A research team led by Berkeley Lab chemist Richard Saykally and theorist David Prendergast, working at the Advanced Light Source (ALS), has shown that, when hydrated in water, positively charged ions (cations) can actually pair up with one another.
“Through a combination of X-ray spectroscopy, liquid microjets and first principles’ theory, we’ve observed and characterized contact pairing between guanidinium cations in aqueous solution,” Saykally says. “Theorists have predicted this cation-to-cation pairing but it has never been definitively observed before. If guanidinium cations can pair this way, then other similar cation systems probably can too.”
Guanidinium is an ionic compound of hydrogen, nitrogen and carbon atoms whose salt – guanidinium chloride – is widely used by scientists to denature proteins for protein-folding studies. This practice dates back to the late 19th century when the Czech scientist Franz Hofmeister observed that cations such as guanidinium can pair with anions (negatively charged ions) in proteins to cause them to precipitate. The Hofmeister effect, which ranks ions on their ability to “salt-out” proteins, became a staple of protein research even though its mechanism has never been fully understood.
In 2006, Kim Collins of the University of Maryland proposed a “Law of Matching Water Affinities” to help explain “Hofmeister effects”. Collins’s proposal holds that the tendency of a cation and anion to form a contact pair is governed by how closely their hydration energies match, meaning how strongly the ions hold onto molecules of water. Saykally, who is a faculty scientist in Berkeley Lab’s Chemical Sciences Division and a professor of chemistry at the University of California Berkeley, devised a means of studying both the Law of Matching Water Affinities and Hofmeister effects. In 2000, he and his group incorporated liquid microjet technology into the high-vacuum experimental environment of ALS beamlines and used the combination to perform the first X-ray absorption spectroscopy measurements on liquid samples. This technique has since become a widely used research practice.
Berkeley Lab’s Rich Saykally has spent much of his career investigating the amazing chemistry of water.
“The XAS spectrum is generally sensitive to the changes in the local solvation environment around each atom, including potential effects of ion-pairing,” Saykally says. “However, the chemical information that one can extract from such experimental data alone is limited, so we interpret our spectra with a combination of molecular dynamics simulations and a first principles theory method.”
Development of this first principles theory method was led by Prendergast, a staff scientist in the Theory of Nanostructures Facility at Berkeley Lab’s Molecular Foundry. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC). The Molecular Foundry and NERSC, as well as the ALS, are all U.S. Department of Energy national user facilities hosted at Berkeley Lab.
With the liquid microjet technology, a sample rapidly flows through a fused silica capillary shaped to a finely tipped nozzle with an opening only a few micrometers in diameter. The resulting liquid beam travels a few centimeters in a vacuum chamber and is intersected by an X-ray beam then collected and condensed out. In analyzing their current results, which were obtained at ALS Beamline 8.0.1, the Berkeley Lab researchers concluded that the counterintuitive cation-cation pairing observed is driven by water-binding energy, as predicted by theory.
Orion Shih, a recent graduate of Saykally’s research group, is the lead author of a paper describing this study in the Journal of Chemical Physics. The paper is titled “Cation-cation contact pairing in water: Guanidinium.” Saykally is the corresponding author. Other co-authors are Alice England, Gregory Dallinger, Jacob Smith, Kaitlin Duffey, Ronald Cohen and Prendergast.
“We found that the guanidinium ions form strong donor hydrogen bonds in the plane of the molecule, but weak acceptor hydrogen bonds with the pi electrons orthogonal to the plane,” Shih says. “When fluctuations bring the solvated ions near each other, the van der Waals attraction between the pi electron clouds squeezes out the weakly held water molecules, which move into the bulk solution and form much stronger hydrogen bonds with other water molecules. This release of the weakly interacting water molecules results in contact pairing between the guanidinium cations. We believe our observations may set a general precedent in which like charges attract becomes a new paradigm for aqueous solutions.”