As leading experts, Spa Vision supplies, procures and consults for the spa, health, beauty and wellness industries. Globally the business works with a broad spectrum of clients including hotel spas, destination spas, wellness centres, day spas, medi spas, salons, yachts, independent therapists and residential homes.
Based on extensive experience and understanding, Spa Vision is well placed to recommend and advise on a number of topics, including the best furniture and treatment table options.
Treatment tables should not only be at the heart of your treatment room but should be at the absolute core of your business. Regardless of the scale or type of business, it is fundamental when delivering treatment-based therapies.
Contemporary treatment tables are beautifully designed pieces of furniture, providing the ultimate comfort for your clients and the very best tools and environment for your therapists. As such they can say much about your business and how important the guest experience is to you as an owner or manager.
The new Masters Collection by Oakworks is all about choice, allowing you to easily select the design, functionality and finishes online. As a result, you get exactly what you want, exactly how you want it.
Developed by our partners Gharieni and Jean-Guy de Gabriac, Wellmassage4D creates a completely new experience of wellness massage. With eight specially pre-programmed positions and the specially developed "Signature Treatment", this new method breathes fresh air into the wellness industry.
Living Earth Crafts have introduced some curve appeal to their impressive collection of spa tables with the new Infinity GT. LEC have been pushing the boundaries of spa design for some time and this is one product recently released which clearly demonstrates that treatment tables should be on display, appreciated and fully admired.
A global spa and wellbeing specialist supplying premium thermal rooms, equipment and furniture.


Ive been recently diagnosed with Squamous Cell Cancer of the cervix , Stage 3. I start Chemoradiation in 2 weeks . Any advice on a list of essentials to put in my care bag and what to expect from treatments ??
welcome to Cancerconnections, and thank you for introducing yourself.
if you look under forums, specific cancers, then your type of cancer, you will find discussions that you can join or start a new topic and chat with others who are travelling the same path as you. You might also be interested in treatments and side effects or the emotional roller coaster.
i am a breast cancer patient and can say that I think all of us hearing that diagnosis, you have cancer, have a similar reaction. It is a stressful time and there is somehow relief in having a plan of action and beginning to move forward.
hope all goes well with treatment and keep us posted. There is much knowledge and support with in this group.
Glad you found us and decided to say Hi. You have great questions about preparing for Radiation.
I'd like to introduce you to nicolem, Cricketclaire, Ravynne, Joni28, 30butfree, Kristen.M.H.. Ladies can you help provide info about what to expect and essentials to pack for treatment?
I wish you all the best with your coming treatment.
Hi Karen Helen, Welcome to the community! There are so many great sources of support and information on this site. I had cervical cancer as well and am just over two years post chemoradiation. From what I was told, people can react differently but I'm happy to share my experience and answer any questions you have. I'll send you a DM!
Karen as far as treatment goes feel free to private message me I would be happy to talk it through. Personally I did chemo radiation brachytherapy and then another round of a trial chemotherapy treatments. Each with their own prosband cons but main advice i can give is take your anti nausea medication even if you feel ok. Its amazing how awful you can feel if you dont and its very hard to backtrack its better to stay on top of it and prevent it. Feel free to message if you want any more details.
My name is Nancy777. I was diagnosed with re- occurrence cervix cancer stage 4 metastasis. Do you mind if I ask what type of chimo is the doctor using for you and how are you filling also if there is any recommendation, I will begin in a couple of weeks.
Glad you reached out here to Karen Helen . Just wanted to let you know that she will see your question if you 'tag' her as I have done.
To do this, simply put the "@" symbol before the user name of the person you are trying to tag, and a list of users will appear for you to select from.
This functionality doesn't like spaces or special characters, so in Karen Helen's case, just type "Karen" and her name will appear in bottom of list.
Thinking of you as you start your chemo. Where are you being treated?
Thank you for your message, I will be treated at Princess Margaret Hospital. I am just waiting on the Oncologist to advised when I will start. By the way, they give you a # of survival in my case or the other option, the natural way, so difficult.


After Easter, we will continue our Geographical studies and learn to understand geographical similarities and differences through the study of human and physical geography of a region of the United Kingdom. We will compare Southport with Keswick. Children will have opportunities to use maps at different scales, relate photos to maps, study aerial views, look at ordnance survey map symbols and look at land use patterns and understand how some of these aspects have changed over time.
The 'Spring Term 2-Summer Term 1' Creative Geography Overview below features how subjects connect through this topic making it exciting and fun to study.
Children are asked to bring their reading book and diary to school each day as this will enable me to provide a comment to inform you when Guided Reading sessions have taken place. Please spend time with your child discussing the setting, characters and development of plot to further their understanding of the text. Books are logged and children are encouraged to clearly note dates and pages read. Feedback from parents/carers is always greatly appreciated.
After Easter, we will focus on developing our tennis skills and train in the hall enjoying rigorous keep fit sessions!
We had a fantastic day recently at Stanley High School. The Young Leaders in Year 8 had organised a range of team games for us to enjoy during a P.E. session. We met Mr Clark the D.T. teacher and he helped us to make our very own mobile phone stand.
We created a 'Fantastic Beast' during an English lesson and shared our ideas with each other learning to improve our writing.
Despite the bitter, cold weather, we ventured around the school's farm and had the opportunity to hold a bearded dragon called Stanley and we fed and stroked some hamsters and guinea pigs. Enjoy looking at the photographs of our visit.
Despite the heavy rain, we had a great day in Chester at the Roman Dewa Experience. Armed with our shields, we marched through the streets towards the Roman Gardens and there, we practised our 'Tortoise' formation.
We cheered on as Celiene (Spartacus) and Mrs Sawyer (Julius) fought in the ampitheatre and then we followed the Roman soldier in command back towards the Dewa Museum for a fun filled afternoon exploring archeological finds and playing Roman games.


The software validates input before applying protection mechanisms that modify the input, which could allow an attacker to bypass the validation via dangerous inputs that only arise after the modification.
Software needs to validate data at the proper time, after data has been canonicalized and cleansed. Early validation is susceptible to various manipulations that result in dangerous inputs that are produced by canonicalization and cleansing.
Implementation Since early validation errors usually arise from improperly implemented defensive mechanisms, it is likely that these will be introduced more frequently as secure programming becomes implemented more widely.
An attacker could include dangerous input that bypasses validation protection mechanisms which can be used to launch various attacks including injection attacks, execute arbitrary code or cause other unintended behavior.
The following code attempts to validate a given input path by checking it against a whitelist and then return the canonical path. In this specific case, the path is considered valid if it starts with the string "/safe_dir/".
The problem with the above code is that the validation step occurs before canonicalization occurs. An attacker could provide an input path of "/safe_dir/../" that would pass the validation step. However, the canonicalization process sees the double dot as a traversal to the parent directory and hence when canonicized the path would become just "/".
To avoid this problem, validation should occur after canonicalization takes place. In this case canonicalization occurs during the initialization of the File object. The code below fixes the issue.
This script creates a subdirectory within a user directory and sets the user as the owner.
While the script attempts to screen for '..' sequences, an attacker can submit a directory path including ".~.", which will then become ".." after the filtering step. This allows a Path Traversal (CWE-21) attack to occur.
Product allows remote attackers to view restricted files via an HTTP request containing a "*" (wildcard or asterisk) character.
Product modifies the first two letters of a filename extension after performing a security check, which allows remote attackers to bypass authentication via a filename with a .ats extension instead of a .hts extension.
Database consumes an extra character when processing a character that cannot be converted, which could remove an escape character from the query and make the application subject to SQL injection attacks.
Product checks URI for "<" and other literal characters, but does it before hex decoding the URI, so "%3E" and other sequences are allowed.
Directory traversal vulnerability allows remote attackers to read or modify arbitrary files via invalid characters between two . (dot) characters, which are filtered and result in a ".." sequence.
Directory traversal vulnerability allows attackers to overwrite arbitrary files via invalid characters between two . (dot) characters, which are filtered and result in a ".." sequence.
These errors are mostly reported in path traversal vulnerabilities, but the concept applies whenever validation occurs.
[REF-62] Mark Dowd, John McDonald and Justin Schuh. "The Art of Software Security Assessment". Chapter 8, "Escaping Metacharacters", Page 439. 1st Edition. Addison Wesley. 2006.


Mulberry 2-Gang Standard size toggle switch wallplate features brass construction with satin finish. Square wallplate measures 4.562-Inch x 4.5-Inch x 0.04-Inch. Wallplate has two toggle switch configuration. It is suitable for architectural purpose. Toggle switch wallplate is UL listed.


Oregon's 2016 Home Rescue Program is for homeowners who are current on their payments.
Oregon's 2016 Hardest Hit Funds goes to homeowners who are current or almost current on their payments.
In 2010, the US Department of Treasury awarded Oregon $220 Million in Troubled Asset Relief Program dollars for foreclosure prevention as part of the "hardest hit" program.
Oregon received this money because of high unemployment. The Treasury awarded Oregon the opportunity to design its own programs in order to respond to the unique housing needs in the state, both rural and urban. Back in 2010 until recently, these funds were available for just the hardest, of the hardest hit counties in Oregon. Now funds are available for people in all counties in Oregon.
Cumulative total of OHSI participates in Oregon organized by county. For more information and quality info-graphics, visit the OHSI website.
Mortgage Payment Assistance – Mortgage Payment Assistance Unemployment program – now open for applications statewide. The Mortgage Payment Assistance Program assists unemployed or financially distressed homeowners by providing full monthly mortgage payments. The program makes up to 12 months of mortgage payments or $20,000, whichever comes first.
d employment or recovered from financial distress to ensure their home loans become, or remain, affordable. Program will pay up to $20,000 to cover past due payments or fees incurred during a period of unemployment or financial distress in order to bring their mortgage current. The program will serve as an exit path for recipients of Mortgage Payment Assistance.
Loan Refinancing Assistance Pilot Project – The Loan Refinancing Assistance Pilot Project assists underwater homeowners who have regained employment or recovered from financial distress, and demonstrate the ability to afford a loan reflective of the current value of their home.


Are you missing out on Agile/DevOps benefits?
While most organisations are committed to the full adoption of both Agile and DevOps, many are struggling with key challenges and missing out on the extensive benefits these practices can have on their bottom line.
A global study from CA Technologies, "How Agile and DevOps Enable Digital Readiness and Transformation" found that, while 75% of respondents recognize that agile and DevOps approaches drive significant business success when implemented together, only a relatively small proportion consider the consistency, depth and breadth of usage of these practices to be high.
The study showcases characteristics of Agility Masters (the top 18%), which are organisations that are farthest along in the full adoption and doing most or nearly all of the right things to make agile and DevOps an essential part of how they function day by day.
These Agility Masters are also more likely to use agile practices across other company functions, so it is unlikely a coincidence that these organisations are seeing a 60 p% cent higher rate of revenue and profit growth, and are 2,4-times more likely than their mainstream counterparts to be growing their businesses at a rate of over 20%.
The study also found that organisations are plagued by similar challenges: culture, skills, program investment and leadership alignment.
It highlights a widespread recognition that implementing agile and DevOps practices across the software lifecycle is not just a matter of new skills and working patterns.
For some, it also requires a significant shift in mindset and behaviour and making those changes is very much a people issue – even at the executive level.
* Relieve time pressures so teams can implement effective agile and DevOps practices (74%).
Respondents also found it very difficult or challenging to find professionals that were familiar with agile methods (68%), had experience with DevOps (77%) and/or had collaborative cross-team working experience (67%).
This clearly indicates a skills gap for the majority of organisations, which requires resources, especially training, to be made available.
"Raising the capability of the engineering team through a well-crafted careers development program will allow us to continue to recruit and retain high calibre individuals," said a chief architect/chief technology officer of a retail business interviewed for the study.


Load testing the ivr and contact centre platforms – promising partnership announced by data synergy and performance lab.
Data Synergy, an Australian vendor of cost-effective and efficient solutions for Performance and Load Testing of enterprise-grade software, announced a partnership with one of the leading software testing companies, Performance Lab, the provider of test automation and performance testing solutions for enterprises across North America and Russia. The companies signed the partnership agreement to help organizations to test the Interactive Voice Response (IVR) and Contact Centre platforms, as well as reduce the cost of testing of contact centre solutions securing the high level of quality.
Read more about related service IVR load testing.
Data Synergy is a Melbourne-based, Australian software development and Contact Centre performance testing company. The company has been created in response to market demand for testing of voice-enabled Telco systems and has asserted the name of a trusted business partner in a series of projects. The core company products integrate seamlessly into a breadth of performance testing tools and provide a complete solution for Omni-channel experience testing.


text:
Vi har dessverre ikke tillatelse til å selge boken til deg i landet du befinner deg i nå.
Stephenie Meyer (forfatter), Ukjent (forfatter), Ellen Archer (oppleser)
The Chemist lydbok
In this gripping page-turner, an ex-agent on the run from her former employers must take one more case to clear her name and save her life. She used to work for the U.S. government, but very few people ever knew that. An expert in her field, she was one of the darkest secrets of an agency so clandestine it doesn't even have a name. And when they decided she was a liability, they came for her without warning. Now she rarely stays in the same place or uses the same name for long. They've killed…
Kan spilles i våre gratis apper for iPhone/iPad og Android
Undertittel The compulsive, action-packed new thriller from the author of Twilight
Forfattere Stephenie Meyer (forfatter), Ukjent (forfatter), Ellen Archer (oppleser)
Forlag Little, Brown Book Group
Utgitt 25 februar 2019
Lengde 17:1
Sjangrer Krim
Språk English
Claire North, Ukjent, Peter Kenny 236,- 207,-
Sally Abbott, Ukjent, Neil Pigot 247,- 217,-
Miss Read, Ukjent, Carole Boyd 177,- 159,-
Horrid Henry's Underpants
Francesca Simon, Ukjent, Miranda Richardson 83,-
Ugly: My Memoir
Robert Hoge, Ukjent, Robert Hoge 247,- 217,-
Mustn't Grumble
Terry Wogan, Ukjent, Terry Wogan 201,- 176,-
The Boy Who Could Fly
Sally Gardner, Ukjent, Andrew Sachs 83,-
Ukjent, Harlan Coben, Tim Machin 201,- 176,-
In this gripping page-turner, an ex-agent on the run from her former employers must take one more case to clear her name and save her life. She used to work for the U.S. government, but very few people ever knew that. An expert in her field, she was one of the darkest secrets of an agency so clandestine it doesn't even have a name. And when they decided she was a liability, they came for her without warning. Now she rarely stays in the same place or uses the same name for long. They've killed the only other person she trusted, but something she knows still poses a threat. They want her dead, and soon. When her former handler offers her a way out, she realises it's her only chance to erase the giant target on her back. But it means taking one last job for her ex-employers. To her horror, the information she acquires makes her situation even more dangerous. Resolving to meet the threat head-on, she prepares for the toughest fight of her life but finds herself falling for a man who can only complicate her likelihood of survival. As she sees her choices being rapidly whittled down, she must apply her unique talents in ways she never dreamed of. In this tautly plotted novel, Stephenie Meyer creates a fierce and fascinating new heroine with a very specialised skill set. And she shows once again why she's one of the world's bestselling authors.

redpajama_set_name: RedPajamaCommonCrawl


text:
Zombie Lake (Jean Rollin, 1981) Review
Find more exploitation reviews here.
"We better face the fact that zombies have declared war!" Originally to be directed by Jess Franco (Sadomania, Oasis of the Zombies), this cheap-as-chips slice of Eurociné cheese was, for many years, disowned by its replacement director Jean Rollin (A Virgin Among The Living Dead). In a remote French town, several years after the end of World War II, something deadly – and bright green – is rising from the so-called 'lake of the damned'. Zombified Nazis, bare boobs galore, and a complete disregard for the laws of continuity dominate this movie, which was destined to be a drinking game only for those with the hardiest of livers...
"Let's say I would like an unusual little yarn about that weird lake of yours." A young woman (Pascale Vital) goes for a stroll through the idyllic Gallic countryside and happens upon a lake. Naturally, this is the perfect time to strip off her kit, sunbathe atop of a fallen tree like a Playboy model, and go for a dip. Unluckily for her, though, beneath the surface – which most assuredly isn't a swimming pool with a bit of black tarp half-hung in the background – lurks a zombie, and not just any zombie, but a zombie Nazi! It emerges from the depths and kills her, and so begins a succession of murders that befall the nubile – and regularly nude – residents of this quaint village.
"Well, the fact is girls are being slaughtered. Get this straight, boy, nobody's going to accuse us!" / "Yeah!" / "Thank you!" After a second death – of a local girl, whose body is delivered to the front door of the town's Mayor (Howard Vernon, The French Sex Murders) – journalist Katya (Marcia Sharif) arrives to uncover the mysteries of the 'lake of ghosts'. As relayed to her by the Mayor (during what must be one of the longest flashbacks in cinema history), the town's lake has a deadly history. As if it wasn't bad enough that black masses, witchcraft, and child sacrifices took place there, the current townsfolk slaughtered a platoon a retreating German soldiers and tossed their bodies into the lake – and now they've returned to exact revenge. As the body count continues to rise, can the villagers fight back, will two outsider policemen be open to the bizarre truth, and can the curse be lifted?
"Wild beast, my ass! Poor idiots. Unbelievable. What do they know?" Suffice it to say, and without an iota of shock in delivering this news, Zombie Lake is a cheap and tacky exploitation movie. However, for all its faults and ridiculous elements (of which there are a great many), it's a lot of fun in that "so bad it's good" kind of way. This isn't to say that the film has no heart to it, because – quite surprisingly for a Eurociné production – there is a rich vein of something deeper buried underneath the pile of bared flesh and day-glow fake blood. During the flashback we see a German soldier (Pierre Escourrou) save the life of a village woman (Nadine Pascale) before they enjoy a fleeting tryst in the mill. Tragically, nine months later, the mother dies after giving birth to Helena (Annouchka) and, of course, the father is slain by the French resistance. Several years later, and with the zombie soldiers rising from the lake, the father returns to the home of his love and meets his child. The cheese factor is high, and yet the delicate – and similarly brief – undead father/living daughter relationship speaks of deeper things. The spectre of war looms like a funereal pall as the horrors of combat literally rise from the depths. Helena is an orphan of the war who finally gets to meet her father – but he's one of the undead – while the father returns only to discover that his lover has died. The fiery climax at the mill, meanwhile, offers up a perverse full-circle as the place of Helena's conception becomes, simultaneously, the site of great violence and eternal relief. Despite all the absurdity, the little girl's plea of "Don't forget me" packs a surprisingly poignant punch.
"The lake! The lake! The lake!" That all said, in the end what Zombie Lake is all about is two simple things: tits and zombie Nazis. The film's crowning achievement (a relative term, of course) is the scene in which an entire female basketball team turn up the lake for a clothing optional splash about, only to be dragged under by the undead platoon. So unabashedly straight forward in its B-Movie goals, the scene was clipped out and inserted wholesale into the clip-show format film Zombiethon, replete with Daniel White's frivolously catchy 'mellow twinkles/dissonant clangs' score. It's amazing that the filmmakers were able to find this many ladies willing to not only strip en masse, but be photographed from below in a swimming pool (the aforementioned piss poor match for the lake's depths). Rewind to the days before broadband Internet, and a videotaped recording of Zombiethon from Sky Movie Max was an eye-opening experience!
"Nothing but apocalypse will reduce them to ashes and give them eternal peace." Enough about all the norks flopping about, though, what about those pesky zombies? The byword for their look would have to be "inconsistent". Evidently green body paint and water don't mix, and as such "continuity" proves to be a term that the production mustn't have heard of, as from one shot to another the one-eyed zombie soldier goes from plain-as-day flesh tone skin to bright green paint. Indeed, some of the other zombies are only green up to their wrists, have prosthetic appliances peeling away from their skin, or have their hair sticking out from underneath poorly-fitting bald caps! For a budget this tight it's almost remarkable they managed as much as they did, as the zombies yo-yo in and out of the lake to regularly spew some red paint onto the necks of unsuspecting villagers. Although, the aerial bombing scene in which the actors on the ground have to react to nothing more than sound effects isn't fooling anyone.
"It may be a waste of time, but I'd like to look into it." Have I mentioned that this film is cheap, and a little bit shoddy in its execution? This, though, is part of the film's charm. The functional, perfunctory direlogue (listen out for the incongruously jaunty "careful" in one of the pub scenes), the dodgy dubbing (and editing), the complete disregard for day/night continuity, giggling extras, crew members traipsing around in the shot (bottom left of frame as the first victim rummages through her bag), power cables and lighting stands left within the frame, and the zombies walking like drunken Brits on holiday with their arms out at a "you want some?" angle, all make for an entertaining watch.
"I fear there's a lot more to this than meets the eye." From the villager's complete, total, and utter lack of surprise at a topless girl bursting into the pub screaming her head off, to the Eurociné idea of foreplay (mashing a closed mouth against some norks), there is much to enjoy with a wry smile. It may be one of a great, great, great many zombie flicks that cashed-in on the epic wake that George A. Romero's landmark film Dawn of the Dead left behind, but Zombie Lake – despite being a complete shambles – is a scrappy, scruffy, and surprisingly fun slab of European B-Movie exploitation. Connoisseurs of cult movies will be in for a treat with this one, but build a drinking game around it at your own risk!
Labels: 1981, bad, drinking game, eurocine, exploitation, film, good, howard vernon, jean rollin, jess franco, movie, nazi zombies, review, screen caps, zombie lake, zombiethon
Flavours of the Month: November 2017...
Fast & Furious 8 - quick review...
Wonder Woman - in review...
Glass Houses Edition: The Walking Dead 8x01 Memes....


THE HAGUE, NETHERLANDS—During the past two years an enthusiastic team of teachers and students have saved almost 40,000 kilos of food, which has been turned into delicious dishes and products. Recently, this team organized a Food Rescue Market to make the new students aware of food waste and to introduce them to the way Hotelschool encounters this. Ten different food rescue companies participated in the market, giving students the opportunity to taste dishes made of rescued food.
The tomato soup of Hotelschool The Hague, made from 4,000 kilos of saved tomatoes, also took a central position at the market. This soup is one of the products which was made within the project PATE, which stands for Practical And Theoretical Education. The aim of the project is to give students the opportunity to create change with a positive impact on the entire Hotelschool The Hague community and society. The UN Sustainable Development Goals (UN SDG) function as a framework for PATE, in order to achieve a better and more sustainable future for all. Hotelschool The Hague also participated in Veggie World recently, where they sold cans of rescued soup. Veggie World is an international fair for vegan products and took place March 9 to 10 at the Jaarbeurs in Utrecht.


text:
Q: Multidimensional Integral by Change of Variable $$\int{\exp((x_2-x_1)^2+k_1x_1+k_2x_2)dx_1dx_2}$$
I can perform the integration of the integral above easily by changing the variable
\begin{align}
u&=x_2+x_1\\
v&=x_2-x_1
\end{align}
Of course first computing the Jacobian, and integrating over $u$ and $v$
I am wondering how you perform the change of variable for 4-dimensional integral like below:
$$\int{\exp\left(\sum_{i=1}^{4}((x_{i}-x_{i-1})^2+k_ix_i)\right)dx_1dx_2dx_3dx_4}$$
Is it something like:
\begin{align}
x_2-x_1&=u
\\
x_2+x_1&=v
\\
x_4-x_3&=p
\\
x_4+x_3&=q
\end{align}
Should this be enough? I think one only needs 4 new variables right? Because I was thinking the integral would be easier if I could do something like:
\begin{align}
x_2-x_1&=u
\\
x_3-x_2&=v
\\
x_4-x_3&=p
\\
x_1-x_4&=q
\end{align}
Or in general, how do you perform change of variable in multi-dimensional case. Should you generally perform it by doing:
\begin{align}
u&=a_1x_1+a_2x_2+a_3x_3+a_4x_4
\\
v&=b_1x_1+b_2x_2+b_3x_3+b_4x_4
\\
p&=c_1x_1+c_2x_2+c_3x_3+c_4x_4
\\
q&=d_1x_1+d_2x_2+d_3x_3+d_4x_4
\end{align}
And what kind of change of variable does one need to perform to perform the integration of such integration easily?

redpajama_set_name: RedPajamaStackExchange


text:
Methamphetamine Research Report
How is methamphetamine misused?
What is methamphetamine?
What is the scope of methamphetamine use in the United States?
How is methamphetamine manufactured?
How is methamphetamine different from other stimulants, such as cocaine?
What are the immediate (short-term) effects of methamphetamine misuse?
What are the long-term effects of methamphetamine misuse?
What are the risks of methamphetamine misuse during pregnancy?
Are people who misuse methamphetamine at risk for contracting HIV/AIDS and hepatitis B and C?
What treatments are effective for people who misuse methamphetamine?
What treatments are under development for methamphetamine use and addiction?
Where can I get further information about methamphetamine?
Methamphetamine comes in several forms and can be smoked, snorted, injected, or orally ingested. The preferred method of using the drug varies by geographical region and has changed over time.37,38,43
Smoking or injecting methamphetamine puts the drug very quickly into the bloodstream and brain, causing an immediate, intense "rush" and amplifying the drug's addiction potential and adverse health consequences. The rush, or "flash," lasts only a few minutes and is described as extremely pleasurable. Snorting or oral ingestion produces euphoria—a high, but not an intense rush. Snorting produces effects within 3 to 5 minutes, and oral ingestion produces effects within 15 to 20 minutes.4
As with many stimulants, methamphetamine is most often misused in a "binge and crash" pattern. Because the pleasurable effects of methamphetamine disappear even before the drug concentration in the blood falls significantly, users try to maintain the high by taking more of the drug. In some cases, people indulge in a form of binging known as a "run," foregoing food and sleep while continuing to take the drug for up to several days.37,38,43
NIDA. 2021, April 13. How is methamphetamine misused?. Retrieved from https://www.drugabuse.gov/publications/research-reports/methamphetamine/how-methamphetamine-misused
NIDA. "How is methamphetamine misused?." National Institute on Drug Abuse, 13 Apr. 2021, https://www.drugabuse.gov/publications/research-reports/methamphetamine/how-methamphetamine-misused
NIDA. How is methamphetamine misused?. National Institute on Drug Abuse website. https://www.drugabuse.gov/publications/research-reports/methamphetamine/how-methamphetamine-misused. April 13, 2021


Use these cute functional planner stickers and washi tapes to mark all the important girl boss duties you need to do. These stickers are ideal for keeping track of important tasks. A perfect gift for yourself or any planner girl you know!


Still hungry for Italy after reading the Abruzzo cover story in the latest issue of Automotive Traveler Magazine? Armin Reindl discovers that a BMW 123d is the ideal car for exploring the gastronomy and history of the Südtirol region in Northern Italy.
The southern side of the Alps stretches from the Brenner Pass on the Austrian-Italian border down to sunny Barbian in the Isarco Valley. South of Innsbruck, Austria and north of Venice, an area ceded to Italy following the First World War, a journey of delicious discovery awaits. Along the Isarco Gourmet Route travelers immerse themselves in the cuisine and culture of the Italian Südtirol.
The trip was made even better for me since I drove it seated at the wheel of a BMW 1 Series Convertible 123d.
Mediterranean and Central European cultural influences meet here in the beautiful Isarco Valley, which boasts a diverse landscape. Dotted with historical monuments and the medieval towns of Sterzing, Brixen, and Klausen, the area is also well known as the home of Eisacktaler wines.
Along the Isarco Gourmet Route, we found great friends and excellent meals presented by traditional restaurants, of which I can recommend quite a few.
Our route took us through the Brenner Pass, then south on the Brenner Road. The road makes its way through Gossensass and past the vaunted Henrik Ibsen spa.
The cemetery features an interesting place of worship: The Miners' Chapel, with a late-Gothic winged altar, is from the period of mining in Pflerschtal, an idyllic valley at the foot of Tribulaun Mountain that today offers hiking and skiing.
Our tour continued to the medieval town of Sterzing, also known by its Italian name Vipiteno. Traditionally Tyrolian, this important commercial center is charming and romantic. Its elegant main street features one of the prettiest town halls in the Südtirol.
Our first stop was the Restaurant Lilie, deservedly one of the best-known establishments in Sterzing. Five centuries have shaped the atmosphere at the restaurant and the Hotel Lilie, in continuous operation since it was established in 1461. Walking through the inn's heavy, vaulted, iron-enforced wood door, you understand why this property is today a protected example of medieval architecture.
Mediterranean cuisine inspires a first-class menu that promises tempting appetizers, fish and meat dishes with tasty sauces, and delicious desserts from its own bakery.
Our journey to the south next passed the Castle Reifenstein. Dating to the 12th century, Reifenstein is one of the most valuable castles in the region. The little hamlet of Trens, with its Gothic church of the Holy Mother of God, is also a popular pilgrimage site.
Our next gastronomic stopover was at the Romantic Hotel and Restaurant Stafler in Mauls. This award-winning gourmet restaurant serves many almost-forgotten South Tyrolean specialties, in addition to creative international classics. The ingredients are fresh from the herb garden on the Stafler family manor, and the wines come from one of the best-stocked wine cellars around. Dining here is traditionally elegant.
You can also visit the lovingly restored Eisacktaler Kramer House nearby with a view of the barn. The adjacent four-star hotel combines medieval roots, historic charm, and modern amenities.
The main road continues to Fortezza, a community that took its name from the impressive fortress built nearby by Emperor Francis I between 1833 and 1838. Laboriously constructed of massive granite blocks, the fort is open to visitors during the summer months.
High on my recommendation list when visiting this area is the Augustinian Abbey of Neustift near Bressanone. The monastery complex includes a beautiful late-Baroque church, a stunning Rococo-style library hall that houses approximately 76,000 manuscripts and volumes, and the pinacotheca or art gallery, in which items ranging from Gothic panel paintings and altarpieces to liturgical treasures and scientific instruments are displayed.
Afterwards, it is impossible to pass the monastery cellar without stopping for refreshment. Where else could an Eisacktaler white wine taste so good?
Next to the monastery is the traditional Hotel Restaurant Brückenwirt. First mentioned around 1152, this Tyrolean inn offers a varied cuisine and a well-stocked cellar showcasing fine regional wines. Specialties include homemade pasta and Tyrolean dishes from ancient recipes. The shady garden invites you for a coffee and cake break, a cool beer, or a glass of wine.
As the oldest town in the Südtirol--its history dates back to 901 A.D.--Brixen boasts numerous sites of historical and cultural significance. Gothic austerity and Renaissance and Baroque splendor harmonize in many facades.
Wide alleys lined with shops and restaurants enliven the downtown area. The town square with its church, cathedral, and adjoining cloister is the spiritual center of Brixen. The white lamb, a symbol of the city, adorns the millennium column opposite the Prince Bishop's Palace with the diocesan and Nativity Museum. The pedestrian zone offers a range of shopping opportunities.
At the end of the main street, you'll encounter the Vital Restaurant La Piazza at the Hotel Goldene Krone, another destination for lovers of fine cuisine. Inspiring the restaurant's design was the image of the hustle and bustle of an Italian piazza where people meet to chat, stroll, eat, and drink. At Restaurant La Piazza, Chef Hans Pardeller will introduce your taste buds to the delights of the Südtirol in a setting that is both modern and vibrant.
Heading 18 kilometers south of Brixen along the banks of the Isarco, we arrived next in Klausen, its narrow, winding lanes and high gabled houses providing an exhilarating drive--especially with the BMW's top down. Chestnut groves and vineyards encircle Klausen and its ancient residences. In his book The Great Happiness, Albrecht Dürer captured this medieval imagery and atmosphere.
Boldly dominating this artistic community is the 10th-century monastery at Säben, which once served as the seat of the diocese before its move to Brixen.
At the southern entrance to Klausen, my recommended destination is the Eagle Room at the Hotel Goldener Adler. The kitchen staff there create excellent meals with a winning combination of traditional Tyrolean cuisine and Mediterranean and international influences.
Don't miss trying a glass or bottle of wine from their cellar. Ask the sommelier for his suggestions, especially from among the lesser-known wineries--and be prepared to enjoy a great meal.
From Klausen, the scenic road winds up to the picturesque town of Villanders. Its village street, captured by the Tyrolean painter Franz von Defregger, is alone worth the trip.
Continuing up the mountain you'll reach the Villanderer Alm, a high alpine pasture with a panoramic view of the Dolomite Mountains--a paradise for hikers.
Returning to the village, we visited the restaurant Capricorn for another gourmet meal. Here--the final stop on our special culinary tour--the historic rooms of the 16th century harmoniously combine history, tradition, and cuisine. The attraction here is the art of von Defregger and Andreas Hofer, and the history surrounding this romantic hideaway. Relax and unwind in the new garden lounge with its expansive views.
Award-winning Chef Alois Unterfrauner understands the presentation of cuisine that is both rustic and Mediterranean in a perfect combination. No wonder the Bertelsmann Big Restaurant & Hotel Guide chose to honor this exceptional establishment as its 2011 Südtirol Restaurant of the Year.
Additional travel information about the Südtirol is available online at Eisacktal.com, Sterzing.com, Klausen.it, and Villanders.info.


Coolest neighboorhood in Madrid. So much to see here, especially if you love street art. Lots of culture and cool places to grab a coffee.
Pilar Albarracin is one of Spain's most fascinating contemporary artists. Her recent exhibition at La Tabacalera is awesome. The use of space creates some unforgettable images. The semi-dark rooms are filled with sensuality and atmosphere. A great art venue of the beaten track.
Really nice artworks and graffitis in an old tobacco factory. Place is open for public but far from being a tourist attraction. There was local people hanging around and spending their evening surrounded by exceptionally inspirational atmosphere.
Super cool alternative place in central Madrid full of interesting graffiti art and creative workshops.
One of the must-visit places in Madrid with graffities, concerts exhibitions and other activities, if you wanna meet with real people and you like this underground style with all of the pros and cons.
The exhibition space of La Tabacalera is amazing. This former tabacco factory has been converted into an exhibition space as well as workshop space for artists.
Get quick answers from La Tabacalera de Lavapies staff and past visitors.


Playaway® is the simplest way to listen to a book. The audio is pre-loaded with 3-5 of Weston Woods' popular, award-winning titles. Simply plug in the ear-buds and enjoy. Or use the universal jack with almost any type of headset or mobility accessory. No Cassettes. No CDs. No Downloads. Just Play!
Don't Let the Pigeon Drive the Bus!/No Dejes Que La Paloma Conduzca El Autobús!


ASHA will be held at the Los Angeles Convention Center in Los Angeles, California, November 9–11, 2017.
It is the premier annual professional education event for speech-language pathologists, audiologists, and speech, language, and hearing scientists.
Bringing together approximately 15,000 attendees, the Annual Convention provides unparalleled opportunities to hear the latest research and gain new skills and resources to advance your career.


One of my favorite fall breads is gingerbread. There's just something about ginger, cinnamon, cloves and rich molasses that make it so delicious.
I love to pair fall foods with my brown transferware. I'm certain it makes everything taste better.
I purchased the transferware several years ago when I came across them at Home Goods. I bought twelve bowls, salad plates, and dinner plates as I thought they would make wonderful Thanksgiving dinner ware.
This is what the pattern looks like. I love the birds with the flower adornment.
This monogrammed 'B' silverplate was my Grandmother's everyday ware, but I keep it tucked away for special occasions. I actually found an entire set of this pattern at a flea market, but without the monogram. I wonder where one would bring silverware these days for monogramming?
Preheat oven to 350 degrees. Coat 9-inch square baking pan with cooking spray.
Combine flour through cloves in a large bowl with whisk. In a separate bowl, combine buttermilk through eggs and stir with whisk. Pour into flour mixture, stirring until moist.
Bake for 45 minutes or until done. Cool on wire rack for 10 minutes and then remove from pan. Enjoy.
The transferware pattern is gorgeous and the mahogany colour makes it look earthy - perfect for Autumn.
omg, i've been eating gingerbread like crazy lately. it's so warm and spicy i just love it. i came across the craziest recipe ever and i can't get enough of it.
your gingerbread looks so great on those jpretty plates.
gorgeous. love brown transferware! I am sure you could take the silverware to a local jeweler for monogramming...???
Trina...the dishes are so pretty, and from Homegoods no less, way to go! They and the Gingerbread were meant for each other...and I'm sure your new dining room will be even more beautiful with these lovely's gracing the table this Thanksgiving.
I have the same plates only mine are in blue!
I absolutely LOVE fall and especially fall breads! (my go-to is pumpkin bread) There's something very cozy about some warm bread and a cup of spice coffee or tea. I can't wait to try this recipe. Thanks!
Your transferware is just divine.
Thanks for sharing your scrummy looking gingerbread recipe, I am most definitely going to make this this weekend!
Thanks for the gingerbread recipe, one of the BEST simple deserts.
I really love your transferware. It's inspired me to be on the lookout for some myself.
The transferware is perfect for this ginger bread - and I love it mixed with your Granny's silver - personally there is nothing better than good silverware to eat with although my husband disagrees. Definitely going to try out your recipe - I have one for ginger cookies which I'll be doing later on my own blog - love ginger! Thanks for sharing - beautiful photographs as always.
I love your brown transferware...it is perfect for this time of year! I think I will have to make some gingerbread now...it looks delicious.
Gorgeous plates!! I have never seen them in brown before and I love them. Really unusual but so pretty! I am just imagining them mixed with a pale pink aftrnoon tea table setting...beautiful!
I always thought of gingerbread as those little men or houses. I am going to give it a try because it sure looks good enough to eat!
Also love gingerbread, how can you not, right?
Very classy presentation on the transferware.
As to monogramming silver -- your jeweler should be able to do it for you. And even replicate the style of your grandmother's monogram. I'm not sure, however, what it would cost.
Thanks for sharing your gingerbread recipe. Now, just add a warm emon sauce!
Sending you a sweet hello from Frog Hollow Farm. The brown transferware looks marvelous with that delicious looking gingerbread cake. I've got to stay away from Home Goods, I'm addicted to their plates and tablecloths!! Ciao, bella!
I am going to try this recipe! It looks and sounds delicious. I have admired your brown transferware for some time now. It is lovely.
Yum! This gingerbread looks wonderful. Will have to make this over the weekend.
You're right - nothing smells better on a fall afternoon than something baked with those particular spices and molasses.
If you take your flatware to a local jeweler I'm sure that he/she could quickly do the monogramming.
My dad loves gingerbread...I should make some for him. I really relate to your comment that fall foods would taste better with these lovely brown plates. I adore finding plates, bowls and silverware at flea markets and tag sales. Some of these treasures are my go to pieces when I eat certain foods. I think this is just a way of adding fun and making the everyday special. I enjoy my treasures, many that I have purchased for very little money, more than pieces that are "worth" more. I also find that since my family had very few pieces handed down, I am creating my own history. I hope you are feeling well and I can't wait for your twins!
I love the fragrance of gingerbread as it bakes in the oven! Your transfer ware is beautiful, isn't it nice to have dishes for special occasions? I have several and I use them all the time. I think you could bring your silver-plate to a jeweler for monogramming. Would you add your grandmothers initial or your last initial? Whatever you decide, enjoy.
I have a serious crush on brown transferware! I love your dishes and yes i do believe they make everything so tasty!!! the recipe looks delicious!
Thanks for sharing the Gingerbread recipe! It sounds delicious. We've been eating Pumpking bread around here. Love the transferware! You could probably find a local jeweler to engrave the silverware, or someone who does awards and such.
My maiden name and my married name both begin with 'B!' So having them engraved would fulfill both past and present.
Love the dishes, silverware and gingerbread!!!
Rest, my dear, time is near!
All wonderful... as usual... and the gingerbread... yumm yumm gnam gnam!!!
I don't know if I told you but I bought a bunch of brown transferware after I saw yours last year. It's all mismatched, which I love, which allows me to pick up odd pieces here and there when I find it. I have everyday dishes that are white and modern and the two pair beautifully.
Yum to both transferware and baking!! The table image you mentioned copying from my blog was from Wm Sonoma (tablecloths) FYI!
Just love transferware, cant have enough of it!
MOTH's just fallen off his Biggest Loser diet with a resounding thud Trina. This is his most favourite sweet treat of all - your recipe looks so moist & packed with flavour.
Yum. Your gingerbread looks heavenly! Thanks for sharing the recipe!
I LOVE transferware. I want to start a collection like you have.
Yummy - thanks for the recipe - I plan to make it soon! I love your transferware.
Great transferware find! The brown is much harder to find in the original. Great snag! Looks stunning against all your white.
A good jeweler will monogram silver for you! Love it all.
Looks and sounds delicious. Can't wait to try it!
My boys gobble down gingerbread whenever my mom comes and makes it. I'll have to give it a try on my own. Love the dishes!
I just love your blog. You are really an inspiration with all your beautiful photos, recipes and decorating tips. Every time you post a recipe and photos, it inspires me to give it a try. Warm gingerbread sounds so good for a cold fall day.
Lovely plates and the gingerbread does look great on them!
My Mother has that silver. Pattern is "Lady Hamilton"
I truly love your blog and the sweet simplicity and elegance your bring to the blogosphere.
You may have already been given advice, but I would check a reputable or locally owned jewelry store for monogramming real silver.
You have totally motivated me to look for some at my local Homegoods.
Martha is right, it is "Asiatic Birds" and so pretty in brown !!It's normally the blue version you find.
I will try the gingerbread recipe- love it.
Have a look and tell me what you think!!
Thank you for sharing the delicious-sounding gingerbread recipe!


Sziget 2013 lineup poll is over, here are the results!
Home > Uncategorized > Sziget 2013 lineup poll is over, here are the results!
The Sziget 2013 lineup poll is now over and, as promised, here are the results of what you guys have voted.
First of all, we must mention that 1050 of you guys have voted in our line up poll this year.
You could vote in the poll starting on June 27, with the voting ending today, August 5.
Now, without further ado, let's take a look at the results of the poll.
To get an even better idea, a graph of the results can also be seen below.
As you can see 32 of the voters thought the Sziget 2013 lineup was excellent (accounting to 3.05%), while 164 thought it was good (15.62%).
26% – 273 votes have been placed for the "Not bad" option, while 355 of the voters (the largest part, at 33.81%) thought that the Sziget 2013 lineup was "Bad". 21.52% of the voters – 226 votes were for the "Very bad" option.
This concludes the Sziget 2013 lineup poll, but Sziget 2013 is just starting, so make sure you have an incredible festival!
Its not surprising… I have been coming to sziget almost every year but this years lineup simply seemed like it had no thought into it (alongside trying to cover the couple of useless indie hype bands).
I really hope it will improve for next year as i really want to keep going.
Hmm, well let's hope that, for the organisers, there's some lessons learned here – cos we'd really love to return to the festival. Sadly, though, I have a feeling that the heavy rock/metal element of the line up has gone for good ….


For the first time, ever, over 111 Olympians from over 39 countries came together to create Olympic art! The IOC President Thomas Bach, the World Olympians Association (WOA) President Joel Bouzou, and even HSH Prince Albert II of Monaco have contributed to the paintings!
This art initiative was organised by Olympians for Olympians by Olympians and created and shown in Gangneung Olympic Village during the 2018 Olympic Winter Games. Olympic athletes using a brush and paint will, collectively, produced 15 paintings, at the rate of one per day, each individual painting representing one of the 15 Olympic winter sports. When combined, the 15 paintings became one painting revealing the Olympic values which are at the heart of this initiative.
Three Olympians, from past editions of the Games, who are also artists, have been working on the field to oversee this project : Roald Bradstock (a two-time Olympic javelin thrower for Great-Britain), Lanny Barnes (a three-time Olympic biathlete and professional artist from the USA.) and Jean Blaise Evequoz (a Swiss artist who competed in fencing in the 1976 Olympic Games).


Prevention & Treatment Though the aviation and health care industries may seem worlds apart, they can learn from one another in implementing simulations to improve safety outcomes.
Contrast that error safety record with health care, which has somewhere between 220,000-440,000 patient deaths attributed to medical error in the United States alone — with 3,000,000 estimated for the entire worl). To be blunt, in the United States, health care is killing hundreds of patients due to error every single day.
While health care has high-fidelity simulation and a CRM training program called TeamSTEPPS to combat this issue, what it doesn't have yet is the Black Box, the crucial component to provide investigators the facts they need to prove what went wrong. When integrated, exposing error will not focus on the individual, but the systems that failed to provide that individual and their teams with the training necessary to be maintain mastery.
One has only to see the rise and success of body cams on police, dash cams in cars and CCTV security cameras in cities to understand that yes, recording during patient encounters is coming to health care. Soon after, simulation will provide the fix that these recording devices expose in clinical spaces.
Those healthcare institutions that can muster the strength to start such programs now will reap massive benefits when the tipping point comes – and will be championed as pioneers, innovators, and thought leaders on an international scale.
The latest health tools are changing monitoring and treatment for heart health, and these new advancements are working to turn the beat around.


Jessica Biel: She had a straight, strong nose that is perfectly proportioned to captivating green eyes and full lips.
Ashton Kutcher: There has been much debate about Ashton having a nose job. There seems to be only a slight change in the tip of his nose over the years, a possible effect of tip refinement surgery.
Anne Hathaway: Sometimes, a strong nose is best to balance other facial features. Anne's nose is very prominent but evens out her big eyes and lips nicely.
Rihanna: Rihanna has definitely had a rhinoplasty to reduce her nostrils and midportion of her nose. She still managed to keep her nose ethnically appropriate, which is suggested for a more natural look.
Kate Middleton: Kate had the most requested celebrity nose in the UK in 2012. The symmetry of her nose, minimal amount of nostril show, and the position between her lip and nose are all very ideal.
A Rhinoplasty is recommended for anyone who desires to improve the overall appearance of their nose. The nose can be altered by removing a hump, reducing the width of the nostrils, altering the tip of the nose, or increasing or decreasing the size of the bridge of the nose.


The outdoor Queenstown Summer Concert this Waitangi weekend will feature Kiwi music legend James Reid of the Feelers as well as New Zealand country pop star Jody Direen and a special appearance from music and comedy duo, the Topp Twins.
The family-friendly concert takes place on Saturday 7 February on Queenstown Recreation Ground in the town centre, the same venue and weekend as the inaugural Hilux New Zealand Rural Games, a two-day celebration of 'sports that built the nation'.
The Topp Twins, who also provide entertainment during both days of the Games, will perform a few numbers with Jody to open the show before James Reid performs. Jody Direen then returns to the stage to headline with her band and deliver a knock-out set including her latest single 'Mine' and recent hits 'Loud' and 'Tattoo' that reached number three in the NZ Official Top 40 single chart.
Born, raised and still living in Wanaka, Jody was recently shortlisted for 'New Oz Artist of the Year' by Australia's CMC Music Awards that take place in Brisbane on 12 March. Her new album 'Jody Direen Breaks Out' will be released in April.
As the vocalist, guitarist and songwriter for The Feelers, James Reid is established as one of New Zealand's most successful musicians. He and The Feelers have sold more albums than any other New Zealand band, making musical history as the first Kiwi act to have four successive Number One albums.
James will be performing Feelers songs at the Queenstown Summer Concert along with work from his first solo album 'Saint'. His band includes local Queenstown bassist, Sam Ross who has just returned from touring the North Island with James and The Feelers.
Doors open at 7.00pm for the concert supported by Wild Buck that starts at 7.30pm and finishes around 10.30pm. Tickets are available in advance from Ticket Direct at a discount from the gate price. Pre-sale tickets cost $35 adults, $15 children/youth (5-17 years) with under-5s free. A family pass for two adults and up to three children costs $85 pre-sale (i.e. up to two children free).


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Why Cardiff City DO need Emyr Huws and how he can offer Paul Trollope's team something different
Many Cardiff City fans really want a new striker, but the arrival of Huws could make a real difference
Huws could bring an extra dimension to the Cardiff midfield
Cardiff City have completed the signing of Emyr Huws . The 22-year-old joins on a permanent deal that sees Paul Trollope start to make good on his promise to get more Welsh talent on the field.
That has gone down well with the Bluebirds faithful, although there are concerns that Huws just adds competition to a pretty well-stocked area of the squad when investment in a proven striker is desperately needed.
If, as rumoured, Wigan use the money to help fund a move for Patrick Bamford then many fans might be left wondering who has got the better deal.
That is probably fair, but it is surely wrong to say Huws will not bring anything new to the table.
He is a lot more direct than most of the current midfielders in the squad and even if his goal scoring record at Huddersfield wasn't terrific, it was decent and he clearly has a bit of an eye for goal.
He can carry the ball into attacking areas and make late runs into the box. That means he should compliment Anthony Pilkington and Lex Immers really well and is the kind of player that was so clearly missing in last night's defeat at Bristol Rovers.
We've taken a closer look at exactly where he might fit into Paul Trollope's system...
In the 5-3-2
One of the factors that makes Huws so appealing is that he can really play in three or four positions across the midfield.
It is certainly an area with plenty of competition, and with the likes of Whittingham, Ralls, O'Keefe and Gunnarsson in the squad, he will not be an automatic starter.
In the 5-3-2 there are probably two roles he could play with ease.
Whittingham looks to have nailed down the deep-lying role and he was sorely missed in Bristol. Aron Gunnarsson did well and was a physical presence but Cardiff really suffered from not having those precise diagonal balls into the wing-backs and over the top of the defence.
Huws will have to compete with the likes of Gunnarsson for a place (Image: Huw Evans Picture Agency)
An explanation of what went wrong for Cardiff City last night and why there's no need for the panic button just yet
Joe Ralls has slotted in front of him so far but that's a role that Huws could easily play. He has the range of passing required and is a comfortable ball carrier. What he will need to show in that role, however, is a willingness to do the dirty work and muck in with the defensive side of the game.
Ralls perhaps does not quite get the credit he deserves for that and when Whittingham plays well he is aided massively by the protection he gets from Ralls and the selfless Stuart O'Keefe.
Most natural for Huws will probably be to play as one of the Number 10s giving Lex Immers the licence to push on and make more runs into the box.
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Immers is probably the most instinctive finisher in the squad and certainly has the best off the ball movement. The League Cup exit showed why that is needed in the final third.
Huws could be perfect for the Number 10 role because he offers a slightly different profile to Cardiff's other midfielders. Eager to take on players and drive towards goal, he could well help speed up Cardiff's attacking play.
There will inevitably be moments of frustration but the Bluebirds have plenty of midfielders tidy in possession and Huws could help spark something extra.
It's the other system used by Trollope in pre-season but one that hasn't been seen in competitive action so far this season.
Featuring two wingers and a centre-forward, the onus is on one of the three central midfielders to shuttle from box-to-box and ensure the attackers aren't left isolated.
Lex Immers played that role and appears to be well suited for it, but Huws' abilities also make him a natural fit.
Lex Immers could be the perfect foil for Huws (Image: Huw Evans Picture Agency)
Cardiff City player ratings v Bristol Rovers: The best and the worst of Paul Trollope's men
He could easily play a little deeper in this system, too, with him and Whittingham or Ralls rotating and taking it in turns to initiate Cardiff counter-attacks. He certainly has the range of passing to pull that off.
So while it is probably true to say Huws is more of a luxury signing than a necessity, it is clear that he can bring a spark to the Cardiff City Stadium.
His arrival really needs to be supported by a new striker but he is an exciting young player whose progress will be fascinating to watch.
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Clays and Clay Minerals (2016) 64 (4): 374-388.
The aqueous chemistry of water films confined between clay mineral surfaces remains an important unknown in predictions of radioelement migration from radioactive waste repositories. This issue is particularly important in the case of long-lived anionic radioisotopes (129I−,99TcO4−,36Cl−) which interact with clay minerals primarily by anion exclusion. For example, models of ion migration in clayey media do not agree as to whether anions are completely or partially excluded from clay interlayer nanopores. In the present study, this key issue was addressed for Cl− using MD simulations for a range of nanopore widths (6 to 15 Å) overlapping the range of average pore widths that exists in engineered clay barriers. The MD simulation results were compared with the predictions of a thermodynamic model (Donnan Equilibrium model) and two pore-scale models based on the Poisson-Boltzmann equation under the assumption that interlayer water behaves as bulk liquid water. The simulations confirmed that anion exclusion from clay interlayers is greater than predicted by the pore-scale models, particularly at the smallest pore size examined. This greater anion exclusion stems from Cl− being more weakly solvated in nano-confined water than it is in bulk liquid water. Anion exclusion predictions based on the Poisson-Boltzmann equation were consistent with the MD simulation results, however, if the predictions included an ion closest approach distance to the clay mineral surface on the order of 2.0 ± 0.8 Å. These findings suggest that clay interlayers approach a state of complete anion exclusion (hence, ideal semi-permeable membrane properties) at a pore width of 4.2 ± 1.5 Å.
How does water confinement in nanopores impact anion exclusion? The answer to this question has important implications for the migration of salts and groundwater through clay-rich rocks (Fritz, 1986; Leroy et al., 2006), the design of engineered nanofluidic systems (Schoch et al., 2008; Bocquet and Charlaix, 2010), the performance of desalination membranes (Richards et al., 2012), and the transport of ions through channels in cell membranes (Nikaido and Rosenberg, 1981; Nikaido, 2003). It also is of importance to high-level radioactive waste (HLRW) management, where the performance of geologic repositories is determined, in many cases, by the migration of anionic, long-lived fission products (129I−,99TcO4−,36Cl−) through nanoporous clay barriers (Tournassat et al., 2007; Altmann, 2008; Claret et al., 2010; Glaus et al., 2011; Altmann et al., 2012).
At present, extant models of anion adsorption and diffusion in nanoporous clayey media postulate either that anions are completely excluded from clay interlayer nanopores (Sposito, 1992; Wersin et al., 2004; Bourg et al., 2008; Churakov and Gimmi, 2011; Tournassat and Appelo, 2011) or that anions are partially excluded from these nanopores in a manner that can be predicted accurately by assuming nanopore water is the same as bulk liquid water, albeit with a lower electrostatic potential imposed by negatively charged clay surfaces (Leroy et al., 2006; Birgersson and Karnland, 2009; Glaus et al., 2013; Tachi et al., 2014). Efforts to test these two competing hypotheses using anion exclusion measurements have been inconclusive because the results of such measurements depend not only on the mechanistic details of anion exclusion in individual nanopores, but also on the pore-size distribution in saturated, compacted clayey media (Tournassat and Appelo, 2011; Tournassat et al., 2016; Tinnacher et al., 2016), which is not yet fully understood (Holmboe et al., 2012).
Molecular dynamics (MD) simulations offer a way out of this conundrum by directly examining the details of anion exclusion in individual clay interlayer nanopores. However, three recent studies that quantified anion exclusion in clay interlayers by MD simulation have yielded contradictory results: one concluded that interlayer water can be treated as having the same aqueous chemistry as bulk liquid water (Hedström and Karnland, 2012), whereas two others reached the opposite conclusion, that anion exclusion in clay interlayers is much greater than would be expected based on the aqueous chemistry of bulk liquid water (Rotenberg et al., 2007b; Hsiao and Hedström, 2015). Consequently, the correct way in which to account for anion exclusion in macroscopic models of ion migration in clay formations and engineered clay barriers remains uncertain (Muurinen et al., 2007; Birgersson and Karnland, 2009; Appelo et al., 2010; Tournassat and Appelo, 2011). The present study aimed to resolve the differences among previous MD simulations. The MD analysis was carried out using montmorillonite as a prototypical smectite clay mineral. This clay mineral contributes predominantly to the specific surface area and surface charge characteristics of most engineered clay barriers and many soil and sedimentary formations. It is also the most widely examined clay mineral in studies of anion diffusion through engineered clay barriers (Bourg and Tournassat, 2015). While the present study focuses on clay interlayers, the results should be relevant to ion and salt migration in other charged nanopores with pore widths below 2 nm.
is the ratio of anion charge concentration in aqueous solution to that of the clay anionic charge (both in moles of charge per kg of water), and the superscripts clay and soln refer to the hydrated clay phase and the bulk aqueous solution phase, respectively. Thus, the anion concentration ratio of the two phases is determined solely by the anion-to-clay charge ratio y and the electrolyte activity coefficient ratio θ. Note that θ = 1 if the electrolyte in each phase has the same mean ionic activity coefficient. The left side of Equation 1 may be very small, indicating anion exclusion, or may be larger than 1, indicating positive anion adsorption in the hydrated clay phase, depending on the values of y and θ. (In general, θ will depend on y.) Consequently, the DE model predicts quite generally that, not only are anions always present in clay interlayers, anions can even swarm there under certain circumstances (Babcock, 1960). This prediction, of course, is a direct consequence of the two model assumptions and thus cannot be considered as a theoretical proof of the presence of anions in clay interlayer nanopores in equilibrium with bulk aqueous solution. Moreover, Equation 1 cannot be applied in a predictive manner, because no accurate model of γiclay exists. Studies of anion exclusion and semi-permeable membrane properties in clayey media have, therefore, routinely used Equation 1 along with the simplifying approximation that γiclay=1 or θ = 1 for all ions (Kharaka and Berry, 1973; Fritz, 1986; Keijzer et al., 1999; Sherwood and Craster, 2000; Revil et al., 2011), an approximation that forms the basis of the well known Teorell-Meyer-Sievers model of ion migration in charged semi-permeable membranes (Wang et al., 1995; Schoch et al., 2008). Brownian dynamics calculations, however, strongly suggest that θ < 1 for a three-layer hydrate of montmorillonite equilibrated with a NaCl solution, whereas θ ≈ 1 in larger interlayer pores (Jardat et al., 2009).
where F is Faraday's constant (96 485 C mol−1), R is the ideal gas constant (8.314 J mol−1 K−1), T is absolute temperature, ε0 is the permittivity of vacuum (8.845×10−12 C V−1m−1), ε is the dielectric constant of water, and ci is the molality of ion i (mol dm−3). The electrostatic potential ψEDL(x) has no thermodynamic significance. In particular, it cannot be substituted for ψclay in Equation 1 because it cannot be measured without relying on ad hoc non-thermodynamic concepts and models (Babcock, 1963; Sposito, 1984).
σ is again the surface charge density (C m−2), and hEDL is the thickness of the region occupied by the EDL (in m). A distance of closest approach of ions to the charged surface can be incorporated into the MEP model by substituting (hEDL − a) for hEDL, thus defining an "ion-accessible EDL thickness" in Equation 3.
Equations 1 and 3 obviously have very similar forms. Because of this similarity, the terms "Donnan model," or "Donnan volume," are sometimes erroneously used to describe the MEP model despite its molecular-scale assumptions (Appelo and Wersin, 2007; Schoch et al., 2008; Birgersson and Karnland, 2009; Tertre et al., 2011; Tournassat et al., 2011; Glaus et al., 2013). The DE model, however, is based on chemical thermodynamics and, therefore, is fundamentally different from the MGC and MEP models, or any other model involving molecular-scale concepts.
Whether a Donnan equilibrium model or a model based on the Poisson-Boltzmann equation is best suited for predicting anion concentrations in clay mineral interlayers cannot be readily answered by comparing model predictions with macroscopic experimental results. Macroscopic data can be fitted to the DE model by adjusting the clay-phase activity coefficients in θ. Since neither the individual activity coefficient values nor the Donnan potential is accessible experimentally, θ cannot be constrained independently. Similarly, macroscopic anion-exclusion data can be fitted with the MGC or MEP model by adjusting the pore-size distribution or the distance of closest approach of ions to the clay surface (Muurinen et al., 2007; Tournassat and Appelo, 2011; Tournassat et al., 2016). Independent information must, therefore, be sought that can be used to test these modeling approaches. In the following, MD simulations are shown to be insightful in this respect.
Simulations of clay-water systems with three interlayer nanopores in contact with a larger mesopore were carried out with the program LAMMPS (Plimpton, 1995). Water molecules were assumed to be rigid according to the SHAKE algorithm (Ryckaert et al., 1977). The clay mineral structure was also assumed to be rigid, as in previous simulations of this type (Rotenberg et al., 2007b; Hedström and Karnland, 2012; Hsiao and Hedström, 2015), but clay H atoms were allowed to move. Recent MD simulations have shown that the equilibrium distributions of interlayer water and ions (but not their dynamics) are insensitive to the motions of clay atoms (Holmboe and Bourg, 2014). Interatomic interactions were described with the SPC/E model of liquid water (Berendsen et al., 1987), the CLAYFF model of mineral-water interactions (Cygan et al., 2004), and the ion-water interaction parameters of Smith and Dang (1994). Van der Waals interactions between unlike atomic species were derived using the Lorentz-Berthelot combining rules. The CLAYFF model includes Van der Waals and Coulomb interaction parameters for atoms in the bulk clay mineral structure and for certain functional groups on the clay edge surfaces (>Si–OH, >Al2–OH), but not for other clay mineral edge groups (>AlOH, >Al–O–Si<). For the present study, CLAYFF-like interatomic parameters were derived for edge >AlOH and >Al–O–Si< groups as described in the Supplemental Materials section.
The cis-vacant structure of montmorillonite was taken from Tsipursky and Drits (1984). Individual clay mineral layers (hereafter referred to as TOT layers) were truncated at the (110) and ( 11¯0) structural planes in order to create edge surfaces, which were then healed by adding −OH or −H groups to under-coordinated edge atoms in order to obtain edge surfaces with zero net proton surface charge (Churakov, 2006). The resulting edge surface structures, which correspond to the AC chains of White and Zelazny (1988), are thought to be the most stable or one of the most stable smectite edge structures (White and Zelazny, 1988; Bickmore et al., 2003; Churakov, 2006; Liu et al., 2014; Newton and Sposito, 2015; Newton et al., 2016). Each TOT layer had a thickness of ~10 Å (ambiguities associated with the definition of the TOT layer thickness are discussed below), a finite length of 45.7 Å in the direction normal to the edge surfaces, and a width of 63.4 Å (effectively an infinite width, because of the periodic boundary conditions of the simulation cell). Each simulation cell contained three TOT layers, three interlayer nanopores, and a larger mesopore (Figure 1). The cell had an initial length of 90 Å in the direction normal to the clay mineral edges (before pressure equilibration), a width of 63.4 Å, and a height of 46.8 Å, 56.7 Å, or 76.5 Å in the direction normal to the clay basal surfaces for simulations of the two-, three-, and five-layer hydrates (referred to hereafter as 2WL, 3WL, and 5WL systems, respectively). Isomorphic substitutions of Mg for Al were randomly distributed on cis octahedral sites. In order to minimize uncertainties associated with the parameterization of edge surface sites, isomorphic substitutions were not allowed to occur near the edge surfaces. The mean number of isomorphic substitutions (108 substitutions randomly distributed between the three TOT layers) was selected in order to obtain a mean basal surface charge density near −0.1 C m−2, a value typical of montmorillonite (Sposito, 1984).
Each simulation cell included 148 Na+ ions and 40 Cl− ions as required to balance the negative surface charge of the TOT layers and establish a NaCl concentration in the mesopore of ~0.5 mol dm−3, ~0.4 mol dm−3, or ~0.3 mol dm−3 in the 2WL, 3WL, and 5WL systems, respectively. The NaCl concentration in the mesopore was chosen such that the MEP model calculations of Hedström and Karnland (2012) (based on Equation 2, with hEDL equal to one-half the width of a clay interlayer nanopore and with a closest approach distance of a = 0) would predict one Cl− ion in each interlayer nanopore, on average, during the entire simulation. Previous calculations have indicated that, at the ionic strengths examined in the present study, the region where the electrostatic potential spills over between the nanopore and mesopore extends ~1 nm from the clay mineral edges into the interlayer nanopores and into the mesopore (Kraepiel et al., 1999; Jardat et al., 2009). These simulated systems should, therefore, be sufficiently large to contain interlayer and mesopore regions that are not influenced by proximity to the clay edge surfaces.
As in the simulations of Hedström and Karnland (2012), a single Cl ion (hereafter denoted Clint) was initially placed in the center of each interlayer nanopore. The three Clint ions were held fixed during equilibration, then allowed to move freely during the simulation. Production runs were carried out in the NVT ensemble (constant composition, volume, and temperature) at T = 350 K with a 1 fs time step. Simulation runs were preceded by 0.5 ns of equilibration in the NVT ensemble, 0.5 ns of equilibration in an NPyT ensemble (constant composition, stress in the direction normal to the edge surfaces, and temperature) at Py = 1 bar and T = 350 K, and another 2 ns of equilibration in the NVT ensemble. Electrostatic and dispersion interactions beyond 15 Å were computed by the Ewald sum method during part of the simulation (22 ns, 17 ns, and 15 ns for the 2WL, 3WL, and 5WL systems, respectively), then by the similarly accurate particle-particle particle-mesh (PPPM) method (Eastwood et al., 1980; Isele-Holder et al., 2012) during the remaining part of a simulation (up to 53 ns, 40 ns, and 38 ns for the 2WL, 3WL, and 5WL systems, respectively).
The contributions of various electrostatic interactions to the potential energy of all Cl− and Na+ ions were calculated using LAMMPS. The contributions of electrostatic interactions with water molecules, clay mineral atoms, and other ions (Na+, Cl−) to the total per-atom potential energy of Na+ and Cl− ions were calculated by canceling the charges of all water atoms, then of all water and montmorillonite atoms during different reexaminations of a trajectory. For the last calculation, where only Na+ and Cl− mutual electrostatic interactions were calculated, the system was not neutral (an excess of Na+ was present due to the TOT layer surface charge) and the computation of a relevant total electrostatic energy (including pairwise and k-space energy contributions) was not possible. Consequently, only pairwise energies were computed with a cutoff at 25 Å.
All Clint atoms left the 2WL and 3WL interlayer space within three nanoseconds of simulation. During the same period of time, Cl− ions from the mesopore entered the 3WL nanopores but did not enter the 2WL nanopores. In the 5WL system, not all of Clint atoms left the interlayer space within the same period of time. According to the concentration maps that were computed after 3 ns of simulation, Cl− has access to 3WL and 5WL interlayers, but not to 2WL interlayers (Figure 2). Note that in the 2WL system, the reported Cl− concentration in the interlayer space is truly zero, not simply a low value that is unresolved by the color concentration scale.
Total Cl− and Na+ concentration profiles and water density profiles (Figure 3) were computed with a spatial resolution of 0.5 Å on the z-axis in the y [65–85 Å] interval, i.e. in the middle of the interlayer nanopores. The calculated water-density profiles correspond to the concentration of O atoms in water molecules multiplied by the mass of one mole of water. The Na+ ions were concentrated in a single peak at the center of the 2WL interlayer space, while two main peaks were present in the 3WL and 5WL interlayer spaces (Figure 3) in agreement with previous MD and Monte Carlo (MC) simulations of Na-montmorillonite with structural charge arising from isomorphic substitutions in the octahedral sheet (Marry et al., 2002; Tambach et al., 2004; Holmboe and Bourg, 2014). The Na density maxima were located at a distance of ~4.5 Å from the siloxane surface O atoms of the TOT layer and separated from the TOT layer by a hydration layer characterized by a water O density peak. Peak positions were consistent with previous studies of clay mineral interlayer nanopores and larger pores (Marry et al., 2002; Tournassat et al., 2009; Bourg and Sposito, 2011). The height of the Na density peaks increased with the number of isomorphic substitutions in the nearby TOT layer, as expected from charge balance considerations. The height of the main water density peak was correlated, but was not strictly proportional, to that of the Na peak, indicating that the structure of the interfacial water layer was significantly influenced by both the clay surface and the adsorbed cations. Few Na+ ions were engaged in inner sphere surface complexes. In the case of Cl, density profiles showed significant anion exclusion even at the mid-plane of the nanopores (Figure 3). The distance of closest approach of Cl− to the plane of O atoms on the basal surface was ~ 3.5 Å. This value coincides with the distance of closest approach of Na+ ions that were not bound in innersphere surface complexes.
At the scale of an individual interlayer nanopore, average concentrations calculated from the MD concentration profiles depend on an arbitrary choice of the boundary between the pore space and the solid phase. The DE model calculations presented in a previous section are based on a molality convention (mol per kilogram of water) while the MGC and MEP model calculations are based on a molarity convention (mol dm−3) with the underlying assumption of a water density of 1 kg dm−3 (note that the effect of temperature on water density was neglected). Consequently, the location of the clay mineral-water boundary was identified based on the choice that yields an average interlayer water density of 1 kg dm−3. The resulting effective TOT layer thickness equals 9.78 ± 0.45 Å for all three systems investigated in the present study (Table 1). Accordingly, average interlayer ion densities were calculated based on interlayer nanopore widths of 5.7, 9.1, and 15.6 Å in the 2, 3, and 5WL systems, respectively (Table 1).
For comparison with the mean interlayer concentrations predicted by MD simulation, interlayer concentrations of Na+ and Cl− were calculated using the MGC and MEP models. The MGC model predictions were obtained by solving the PB equation (Equation 2) numerically using the values of σ and cisoln from the MD simulation as input parameters (Table 2). The distance of closest approach of ions to the solid surface was identified based on the MD concentration profiles, using either the location of the 'foot' of the Na+ density profiles or the location of the Na+ density peak (Figure 3 and Table 1). In the case of the 2WL system, the second option was not available because only one Na+ density peak was present. The MEP model calculations assumed that the EDL filled the entire interlayer pore space and involved the same assumptions as the MGC model regarding the distance of closest approach of ions to the clay mineral surface (Table 2). Predicted Na+ and Cl− density profiles were converted to average concentrations per mass of interlayer water in order to ensure consistency between different results.
The per-atom electrostatic energy corresponds to the coulomb energy attributed to each individual Cl− (Na+) ion in the system. For the 2WL system (Figure 4), the computation of the per-atom energy for Cl− in the interlayer space was not possible because chloride did not enter the interlayer space during the simulation. On the other hand, the total per-atom electrostatic energy was the same in the mesopore as in the interlayer in the 3WL and 5WL systems (Figures 5 and 6). The most remarkable outcome of this calculation is that, in the 3WL and 5WL systems, the electrostatic energy arising from Cl− solvation was much higher (less favorable interaction) in interlayer nanopores than in the mesopore. The opposite effect was not observed in the case of Na+; electrostatic interaction of Na+ ions with water molecules was approximately equally favorable in the interlayer nanopores as in the mesopores. A similar asymmetry in Na+ and Cl− solvation energies has been observed in model polar nanopores and ascribed to hindered orientations of confined water molecules hydrating Cl− in nanopores (Crozier et al., 2001). As expected, interactions with other ions in the interlayers were attractive in the case of Cl− and repulsive in the case of Na+ (lower row in Figures 4, 5, and 6).
In the case of the 2WL hydrate, no Cl− ion entered the interlayer space during the course of the simulation, in agreement with the modeling results of Rotenberg et al. (2007b), but in disagreement with those of Hsiao and Hedström (2015). The Cl− concentrations expected from the energy barriers predicted by Rotenberg et al. (2007b) or Hsiao and Hedström (2015) for bulk NaCl concentrations similar to those obtained in the present study are given in Table 3, together with the average number of Cl− ions expected in the interlayer space during the course of an entire simulation. The simulations were carried out at the same temperature (350 K) as the simulations of Hsiao and Hedström (2015) and with similar simulation times (50 ns vs. 100–200 ns) and volumes (27×104 Å3vs. 15×104 Å3), thus ensuring roughly equally reliable output statistics. The fact that Cl− ions did not enter the interlayer space cannot, therefore, be attributed to a lack of convergence in the present simulation, as Hsiao and Hedström have postulated to explain the difference between their results and those of Rotenberg et al. (2007b).
The mapping of the per-atom electrostatic energy contributions evinced the major role played by solvation in inhibiting the entry of Cl− into the interlayer space. This effect was particularly pronounced in the 2WL system, perhaps because a significant fraction of the water molecules associated with the water density peaks nearest to the clay surfaces (i.e. most of the interlayer water in the 2WL hydrate) were engaged in solvating Na+ outer-sphere surface complexes while also donating a hydrogen bond to the siloxane surface O atoms (Marry et al., 2008; Bourg and Sposito, 2011). In short, water located in the first monolayer on the clay surfaces had a very different structure from bulk liquid water (Low, 1979), and this difference became acute in the case of the 2WL hydrate. These findings are consistent with the hypothesis formulated by Hsiao and Hedstrom (2015) that differences in solvation energy play an important role in inhibiting the entry of Cl− in the interlayer space.
Molecular dynamics simulations are well known to be sensitive to the choice of parameters used to describe interatomic interactions. Consequently, differences in the extent of anion exclusion predicted by Rotenberg et al. (2007b) and Hsiao and Hedström (2015) may reflect differences in the parameterization of interatomic interactions in these two studies. The present work used the same interatomic potential models as Hsiao and Hedstrom (2015), namely, the CLAYFF and SPC/E models. To the best of the present authors' knowledge, the only major methodological difference between the present simulations and those of Hsiao and Hedstrom (2015) is that these latter authors treated the negative structural charge of the clay mineral particles as uniformly distributed over all octahedrally coordinated atoms in the clay mineral structure. In the present simulations, the negative charge arising from each Al → Mg isomorphic substitution was assigned to the site of substitution and its six surrounding O atoms in accordance with the original CLAYFF model. The treatment of clay mineral negative structural charge used in the present study was derived from quantum mechanical calculations of the electrostatic potential near clay mineral surfaces (Cygan et al., 2004), which predicts interlayer water and ion distributions and dynamics in excellent agreement with experimental results (Bourg and Sposito, 2010; Ferrage et al., 2011; Marry et al., 2011). The present results do not allow an accurate quantification of the height of the energy barrier opposing Cl− entry into the interlayer space of the 2WL hydrate, but strongly suggest that this barrier is greater than that predicted by Hsiao and Hedstrom (2015).
The numerical solution of the PB equation for the 3WL and 5WL hydrates was consistent with the average interlayer Na+ concentration and with the interlayer Na+ concentration profile predicted by the MD simulations (Figure 3). This close correspondence was particularly true if the distance of closest approach of ions to the clay mineral surface was identified with the foot of the Cl− density profiles, which yields a = 2.0±0.8 Å. This predicted a value was in good agreement with the range of values regarded as a typical ion size in studies of ion adsorption (a =1.8 to 2 Å) (Sposito, 1992; Kim and Netz, 2006) and with the hydrated radii of Na+ and Cl− (1.7 and 2.0 Å, respectively) (Jardat et al., 2009). The agreement between PB calculations and MD simulation predictions was somewhat worse in the case of the Cl− concentration profiles than in the case of the Na+ profiles (Figure 3), perhaps reflecting the poorer statistics for interlayer Cl concentrations or the influence of short-range ion-ion interactions (and possibly ion-water interactions, as noted above) that are not accounted for in the PB equation. Nevertheless, reasonable quantitative agreement was found (Table 2). These calculations further showed that, for the systems examined, the average interlayer Na+ and Cl− concentrations predicted with the MGC and MEP models were essentially identical, i.e. a full numerical resolution of the PB equation was not necessary to predict average ion concentrations in the nanopores. Instead, predicted interlayer anion concentrations were primarily sensitive to the distance of closest approach used in the MGC or MEP models, the best fit being obtained with a distance of closest approach intermediate between those obtained using the 'closest approach' and 'Na peaks' approximations. The similarity of the MGC and MEP models in the case of monovalent ions is consistent with recent predictions of the density profiles of Na+, Cl−, and Br− (but not Ca2+) in a 31.5 Å-wide clay interlayer nanopore (Tinnacher et al., 2016).
According to Hsiao and Hedstrom (2015), solving the Poisson-Boltzmann equation in order to model the behavior of ions in clayey media is not necessary, because the use of the Donnan equilibrium (DE) model is warranted for compacted clay systems. A strict application of Henry's Law (and, hence, of the DE model) to clay systems would require that the counterions be dissociated fully from the mineral surface, such that mean ionic concentrations in the hydrated clay phase be unambiguously determined (Babcock, 1963). The present MD simulations were carried out at a relatively high salinity and, therefore, the simulations cannot determine whether Henry's Law is valid for counter-ions in a clay system. However, MGC model calculations (Sposito, 1992), X-ray reflectivity experiments (Schlegel et al., 2006; Lee et al., 2010, 2012), and MD simulation studies (Marry et al., 2002; Rotenberg et al., 2007a; Holmboe and Bourg, 2014) have provided strong evidence that cations remain condensed at clay mineral–water and mica–water interfaces, even under bulk solution conditions approaching infinite dilution. The results presented here indicate MGC model calculations and MD simulations are mutually consistent, even in highly compacted clays, and, therefore, suggest that the DE model cannot be valid, even in highly compacted clay.
The PB model does not rely on the validity of Henry's Law. Consequently, the MEP model predictions are similar to those of the DE model and it remains valid within the limits of the underlying molecular-scale hypotheses and approximations. The interlayer pore scale of the 3WL system can be considered as the lower limit for water content in this model. Below this scale, the mean force potential that applies to Cl− ions entering the interlayer region cannot be approximated using mean field theories, because Cl− is significantly more weakly solvated by confined water than by bulk liquid water. Within the context of the MEP (or MGC) model, this effect can be modeled in a straightforward manner by accounting for the distance of closest approach of ions to the clay surface, a ~ 2 Å.
The present MD simulations demonstrated that anion exclusion from clay interlayer nanopores is significantly greater than expected from mean field theories, such as the modified Gouy-Chapman (MGC) or the simplified mean electrostatic potential (MEP) models. The calculations showed that this effect can be viewed as arising from the weaker solvation of Cl− by confined water than by bulk liquid water and it can be modeled by accounting for the closest approach distance of ions to the clay surface, a ~ 2 Å. Calculations reported here further suggest the existence of a threshold value in nanopore width below which Cl− cannot readily access clay interlayer nanopores.
Comparison of the MD simulation results with the underlying hypothesis of the Donnan model established that the Donnan model cannot be applied to clay-water mixtures because these systems do not satisfy the two basic assumptions made about the behavior of ions in a Donnan system. This problem is related to the geometry of the charged surfaces (infinite plane), which leads to counterion condensation in the vicinity of the surface (Sposito, 1992), thereby preventing the full dissociation of Na+ ions from the surface at infinite dilution required by the Donnan model. Although a mean electrostatic potential model derived from the Poisson-Boltzmann equation may be equivalent numerically to the Donnan model, it is fundamentally different in terms of the underlying hypotheses.
The ability of Cl− to enter clay interlayer nanopores decreases sharply as pore size decreases from 9.1 Å (3WL hydrate) to 5.7 Å (2WL hydrate). This finding should be taken into account when predicting the membrane properties of compacted clay materials. The present results suggest that clay materials may behave as nearly ideal semi-permeable membranes under conditions where only 2WL interlayer spaces (or inter-particle pores of similar width) connect the diffusion paths between larger pores, in agreement with recent experimental results by Chagneau et al. (2015).
This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, of the U.S. Department of Energy under Contract DE-AC02-05CH11231. C. Tournassat acknowledges funding from L'Institut Carnot BRGM for his visit to the Lawrence Berkeley National Laboratory, and from the CNRS-NEEDS project TRANSREAC. G. Sposito acknowledges funding from the University of California at Berkeley under the auspices of a Chancellor's Professorship. The research reported in this paper used resources of the National Energy Research Scientific Computing Center (NERSC), which is supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC-02-05CH11231.
This paper is published as part of a special issue on the subject of 'Computational Molecular Modeling'. Some of the papers were presented during the 2015 Clay Minerals Society-Euroclay Conference held in Edinburgh, UK.
Snapshot of the simulated 2WL system with layer edges bordering a mesopore, highlighting the difference in concentrations of Na (small dark blue spheres) and Cl (large light blue spheres) atoms in the interlayer nanopores and in the mesopore. Water O and H atoms are shaded. The system is periodic in all directions.
The Cl− (left) and Na+ (right) concentration maps in the 2WL, 3WL, and 5WL systems (from top to bottom). The colored concentration scale is in mol dm−3. White areas correspond to regions where no Cl− or Na+ ions were present during the entire MD run.
Concentration profiles in the interlayer region (y [65–85 Å]) for the 3WL (left) and 5WL (right) systems. Top: Na+ concentration (red) and water density (O atoms, blue) profiles; the orange bar indicates the number of Mg for Al substitutions in the TOT layer (arbitrary unit). Middle: comparison of Na+ (red) and Cl− (green) MD concentration profiles (plain lines) with the PB prediction (dotted lines) assuming a distance of ion closest approach to the surface of 3.5 Å from the most external oxygen atoms of the TOT layer. Bottom: same calculations but with an ion closest approach distance to the surface corresponding to the maximum Na+ concentration peak position.
The Cl− (left) and Na+ (right) electrostatic energy maps for the simulation period 3 ns to 50 ns in the 2WL system. The energy scale is in eV. The top row shows the total electrostatic energy per ion. The middle row shows the electrostatic energy arising from interactions with water molecules. The bottom row shows the electrostatic energy arising from short-range (< 25 Å) interactions with other ions.
Same as Figure 4 for the simulation period 3 ns to 40 ns in the 3WL system.
Same as Figure 4 for the simulation period 3 ns to 38 ns in the 5WL system.
Layer charge, mean Na+ and Cl− concentration in the three interlayer spaces for the three systems (2WL, 3WL, and 5WL), and associated NaCl concentration in the bulk liquid. Interlayer ion concentrations were calculated either from our MD simulation results or by applying the MGC or MEP models with an accessible volume corresponding to the 'closest approach' hypothesis as used in Table 1 (values in parentheses correspond the value calculated with the 'Na peaks' hypothesis). All concentrations were normalized to the effective interlayer thickness corresponding to a water density of 1 kg dm−3. Note that the computed surface charge was higher than the overall surface charge because no isomorphic substitution took place near the edges, meaning that the surface charge in the middle part of the layers was larger than the average charge of the layers. Values highlighted in bold were averaged over the three interlayer nanopores in each simulation. NA: Not Applicable.
Chloride concentration expected in the 2WL hydrate interlayer space according to the energy barriers predicted by Rotenberg et al. (2007b) and Hsiao and Hedström (2015). The last column indicates the expected average number of Cl− ions in the interlayer space during the course of the entire simulation. Reported energy barriers were calculated either by umbrella sampling Rotenberg et al., (2007b) or by both umbrella sampling and unconstrained MD simulations by Hsiao and Hedström, (2015).