Application of Hard-Soft Acid-Base Theory

Application of Hard-Soft Acid-Base Theory By Manolis J. Manos and Mercouri G. Kanatzidis Report Feven Teclemichael Hard-Soft Acid-Base Theory in Action: A New Ion-Exchange Material for Sequestering Heavy Metals The human body consists 75 percent of water, clean water is one of the prime elements responsible for life on earth. However, today many people drink water that is far from being pure. Inorganic minerals such as mercury (Hg), lead (Pb), and cadmium (Cd) are some of the powerful pollutants that make water unsuitable for human consumption and other living organisms. Over the years, a lot of effort has been gone into making drinking water as safe as possible by testing different methods to remove Hg2+, Pb2+ and Cd2+ ions from polluted water Some of the traditional ways of removing the above mentioned heavy metal ions is using oxidic inorganic ion-exchange materials such as Zeolites, clays and carbon activated adsorbent. Although these materials can remove heavy metals, they have a low selectivity and weak bonding affinity for heavy metal ions. Sulfide minerals such as FeS2 also have a low selectivity for heavy metals due to their property of instability in natural environment (i.e. when exposed to air and water it gets oxidized). To overcome these problems novel sorbents such as resins, organoceramics and mesoporous silicates as well as the recently noted mesoporous carbon material with thiol groups has been developed. However, these materials only showed a high selectivity for Hg2+. Similarly, Fe3O4 nanoparticles coated with humic acid also showed a reasonable but low selectivity for these soft heavy metals. On the other hand, unlike iron -based sulfides sulfide-based ion exchangers have a higher ability to remove heave metals ions regarding their functional group and surface property. This is due to their higher affinity of their soft basic framework for soft Lewis acids (e.g. Hg2+, Cd2+,Pb2+). One of sulfide-based material that has been found to be a high candidate for heavy metal ion remediation is K2xMnxSn3-xS6 (x=0.5-0.95) (KMS-1). K+ existing as +2, Mn as +4, Sn as +6 and S as -2 oxidation states. The layer structure of this material is built up by edge-sharing Mn/Sn S6 octahedral with Mn and Sn atoms occupying the same crystallographic position and all sulfur ligands being three-coordinated. K+ ions are found between the layers and are positionally disordered (Manos Kanatzidis, 2009). This material contains highly mobile K+ ions in their interlayer space that can easily be exchanged with other heavy cations (Manos Kanatzidis, 2009). KMS-1 is inorganic ion-exchanger that exhibits an excellent thermal, chemical and radiation stability in aqueous and atmospheric environments that can not be easily achieved with organic compounds. This material has previously been proved to be an excellent sorbent for strontium ions. Based on Manolis J. Manos and Mercoui G.Kanatzidis de tailed research this material has a extraordinary capacity to remove Hg2+ Pb2+, and Cd2+ very rapidly from water than any ever-known sorbent materials and has a high selectivity that allows their concentration to be reduced to well below the government allowed safe drinking levels under broad pH range (Manos Kanatzids, 2009). Based on this study this materials structure allows a rapid ion-exchange kinetics of the intercalated K+ ions with soft Lewis acids and binds to these soft heavy metal ions through a strong covalent interactions Metal-Sulfide framework of KMS-1. The experiment of ion-exchange is done by isolating a filtered polycrystalline material from the mixture of A(NO3)2.yH2O (0.07mmol) (A=Hg, Pb, Cd) with 20ml of water and a solid KMS-1 90.07mmol, 40mg). The filtrates were analyzed for their heavy metal content by using a coupled plasma-mass spectroscopy (ICP-MS). The energy-dispersive spectroscopy (EDS) data of the study has confirmed the removal of K+ ions as well as t he binding of the heavy metal ions. Two analyses were done to see how the interlayer spacing changed and to obtain information about the structural change after metal ion exchange material. These are the Power X-ray diffraction (PXRD) measurement and the Pair distribution function (PDF) analysis. PXRD data of Hg2+ exchanged material showed a decrease in the interlayer distance after the ion exchange. It changed from 8.51 ºÃ‚ ® to 5.82 ºÃ‚ ® this is because of the smaller size of Hg2+ compared to K+ as well as due to the strong covalent bond formed between Hg-S. This analysis also revealed the presence of two layered phases. These layers existed with interlayer spacing of 8.81 ºÃ‚ ®-8.09 ºÃ‚ ®. This information was also found in the two hydrated Pb2+ species analysis. Alkaline earth ions have a great tendency to be hydrated and this results for the Pb2+ exchanged materials. The Thermogravimetric analysis (TGA) data for exchanged samples revealed the presence of 1-2 H2O molecu les per formula unit. The process of Cd2+ exchange was different than Hg2+ and Pb2+ processes. Hg2+ and Pb2+ exchanged only with K+ ions where as Cd+2 exchanged not only with k+ but with Mn2+ ions of the layers as well. The EDS data of KMS-1 showed no detection of Mn even using ICP Mn ion was not identified. The molar ratio of Cd2+: KMS-1 in the exchanged material was found to be ~2 with a formula of Cd1.8Sn2.1S6 and no sign of Mn2+ ion. Cd2+ exchange also yielded in a colour change from dark-brown to orange-red. The TGA data of Cd2+ exchanged material revealed the presence of partially hydrated Cd2+ cation ~1-1.5 water molecules per formula unit and the PXRD indicated the consistency of interlayer contraction ~2.2 ºÃ‚ ® relative to KMS-1 strong Cd-S bonding interactions in the interlayer space (Manos Kanatzidis, 2009). Solid state near infrared-ultraviolet-visible (NIR-UV-Vis) spectroscopic studies was important to examine the intercalation of metal ions in pristine KMS-1. The expected covalent interactions between the sulfur atoms and intercalated cations are KPb(exchanged)>Hg(exchanged). The Cd2+ exchanged material band gap energy was measured to be 1.96ev; this result is consistent with its colour change from dark brown to orange-red. To assess the Hg2+, Pb2+and Cd2+ removal capacity of KMS-1, ion-exchange equilibration studies is performed using the batch method which is done in a V: m ratio of 1000:1 at a room temperature of pH 5. The ICP-MS determined the initial and final concentrations of the heavy metal ions. In order to have enough metal ions to saturate the exchange sites of K2xMnxSn3-xS6 (x=0.95) (the molar ratio M2+/KMS-1 was ~1), the initial concentration of Hg2+ and Pb2+ was much higher than Cd2+ since they can decompose to HgS or PbS unlike Cd2+. The Hg2+ and Pb2+ ion-exchange equil ibrium data was fitted with the Langmuir isotherm model expressed as , where q (mg/g) is the amount of the cation adsorbed at the equilibrium concentration Ce (ppm), qm is the maximum adsorption capacity of the adsorbent, and b (L/mg) is the Langmuir constant related to the free energy of the adsorption. The maximum ion-exchange capacity qm of KMS-1 (x=0.95) was determined to be 377 mg/g and 319 mg/g, respectively. The affinity for the metal ions can be expressed in terms of the distribution coefficient Kd value. Kd coefficient describes the sorption/desorption propensity of a compound for a material. For Hg2+ and Pb2+ the Kd values were found in the range 3.50*10^4-3.90*10^5 mL/g and 1.29*10^5-1.40*10^6 mL/g, respectively. The equilibrium exchange data of Cd2+ was fitted with the Freundlich model: q= KfCe(1/n), where Kf is the Freundlich constant. The maximum capacity was calculated by averaging Cd2+ uptake values that corresponds to the saturation of the exchange sites of KMS-1 an d it was found to be 329mg/g or 2.93mmol/g which is close to the theoretical value of 3.18mmol/g. The Kd value obtained for Cd2+ was 1.16 to 1.37*10^7mL/g which is larger compared to the initial concentration between 204.4 and 136.3ppm. The effect of pH on Hg2+ and Pb2+ adsorption was studied in the range of 2.6-9.4 and Cd2+ adsorption was tested in the pH range of 0-9, while taking into account that the pH of contaminated ground water and nuclear waste may vary in acidity. The Hg2+ ion exchange study of KMS-1 indicated a significant uptake at pH>4(Kd=1.1-1.3*10^4mL/g) compared to at pH~2.6 (2.3*10^5mL/g). For Pb2+ the maximum Kd value calculated for KMS-1 is at pH 3.7. The Kd value for Cd2+ revealed a remarkable affinity of KMS-1 under strong acidic condition (pH=0). For comparison, thiol-functionalized sorbents displays a loss of ~40-50% of their Cd2+ adsorption capacity at 3+ and Ca2+ was also examined for selectivity. The results showed a high selectivity for Hg2+ and Pb2+ even for Cd2+ since KMS-1 showed 86-88% removal of Cd2+ removal in the presence of 1M Na+ or Ca2+. Competitive-exchange Hg2+, Pb2+ and Cd2+ -Na+ experiment was performed in a very high or very low initial concentrations, these cations showed that KMS-1 has the ability of removing all 3 metal ions from solutions and shows a similar selectivity for solutions that contain a mixture of Hg2+, Pb2+ and Cd2+ in low initial concentrations. In final concentrations of the metal ions were found to be well below the acceptable levels for drinking water (Manos Kanatzidis, 2009). To check how capable is KMS-1 to select heavy metal ions under realistic environment, it was tested with drinkable water that has a pH of 6.5 and was contaminated intentionally with high levels of Hg2+, Pb2+ and Cd2+ that has excess amount of Na+, Ca2+, Mg2+ than the heavy metal ions. The results showed that within 40 min KMS-1 lowered the concentration of Hg2+, Pb2+ and Cd2+ below their acceptable limits. A high absorption of heavy metal ions by KMS-1 was observed by sonicating them for 30-60min when the particle size of pristine samples was reduced to à ¢Ã¢â‚¬ °Ã‚ ¤5 µm. This finding shows that pre-treated KMS-1 samples have a high ability to reduce the concentrations of heavy metal ions well below their acceptable levels after 2 min of solution/KMS-1 contact. These results prove that KMS-1 is highly capable of selecting and filtering contaminated waste water that contains traces of heavy metal ions. Mg-analogue of KMS-1 is developed to explain the concerns regarding Mn leaching (0.3-0.8% of the total manganese content at pH~5-8) during the use of KMS-1 to purify waste water. The analogue developed is denoted as KMS-2 (i.e. K2xMgxSn3-xS6 (x= 0.5-0.95)). The study indicated that KMS-1 and KMS-2 have not different capacity to purify heavy metal ions from water and have identical PXRD pattern. According to the study supporting information Mg2+ is non-toxic and a large level ppm of Mg2+ in water is acceptable. Since regeneration of exchanged materials is not possible under highly acidic environment of KMS-1 compounds, a test can be formulated to see if the exchanged materials can be considered as permanent waste forms without the need of secondary treatment. The study shows that first treatment results revealed no leaching of Pd2+ after its hydrothermal treatment at pH of ~7 or 4.8 for 24hrs. Similarly Hg2+ and Cd2+ only showed 0.05 and 0.09% of leaching, respectively. Whereas, the thermal treatment of Hg-laden samples for 60hrs at 450 °C showed 93% of leaching which is almost all the Hg2+ content has been regenerated. This process can be used to recover mercury element. This study showed the high efficiency of KMS-1 to absorb heavy metal ions and proved that it is one of the only materials that has a high capacity for Hg2+, Pb2+ at acidic condition (pH~3) and alkaline condition (pH~9), and highest for Cd2+ among all other state-of-the-art sorbents even at pHà ¢Ã¢â‚ ¬ °Ã‚ ¤0. However, thiol-functionalized mesoporous silicates resulted in a low absorption for Pb2+ at pH2 (layered sulfide) and thiol-functionalized sorbents is compared, KMS-1 has the highest because it is stable in water and atmosphere, on the other hand LiMoS2 and thiol-functionalized have less absorption capacity because they have instability nature under aerobic conditions. KMS-1 is a sulfide layered metal that exhibits a high capacity and highly specific ion-exchanger for the removal of soft heavy metals by replacing K+ in between the metal sulfide layers of KMS-1. The driving force for heavy metal ion-exchange is the strong heavy metal ion-sulfur bonds in addition to the facile ion diffusion and access of all internal surfaces of layered metal sulfides. It is a low-cost promising material that can be used to purify waste water by reducing the concentration toxic heavy metal ion (i.e. Hg2+, Pb2+ and Cd2+) well below acceptable limits for drinking water. HSAB theory elaborates that soft acids prefer bonding with soft bases, and the adduct of the result tends to form a covalent bond. Equivalently hard acids prefer bonding with hard bases, and their adducts form a stronger bond called ionic interactions (electrostatics attraction). This study provides a practical application of HSAB theory concepts. It proved that HSAB theory can be useful to identify compounds that can potentially be used in predicting toxicant-target interactions and the bonding mode can be determined using the principle. The main purpose of the study was to explore or discover a material that can reduce or remove major water pollutants such as Hg2+, Pb2+ and Cd2+.This study experiment reported a sulfide layered metal material that can rapidly remove toxic heavy metals from water called KMS-1. As per HSAB rule sulfur is considered to be a much softer base element therefore it prefers to bond with soft acid (e.g. Hg2+, Pb2+ and Cd2+).

Influence of Mass Media on Teenagers

Influence of Mass Media on Teenagers Mass media plays a significant role in today’s world. It broadcasts informationas fast as possible as well provides entertainment to massive audiences. Mass Media comprises of press, television, radio, books and the Internet. Media is one of the most influential aspects of our lives. By creating a certain type of message, media can manipulate people’s attitude and opinions. Over the years, as technological advances have taken place this type of communication has become very easy and feasible to have. Almost every household now owns an internet connection, television or a cell phone etc. This has led to a widespread usage of mass media, especially among the teenagers. The fact that there was a time when the internet, television and cell phones were considered a necessity but now they seem to be more of a commodity teenagers seem addicted to pretty much explains that there is bound to be a downside to the influence mass media has on teens. The teenagers of today seem too engrossed in watching their favourite shows on television or using social media applications on their phones or computers that they are slowly losing touch with reality. They have become addicted. There are many consequences to this unhealthy addiction. One becomes lazy and does not feel the need to get up and do something productive. It leads to obesity and tiredness. It also leads to unhealthy consumption of junk or fast food. I say this from my personal experience, as I always feel the need to have pizza or chips along with a beverage when I’m watching a show or a movie. Teenagers also tend to spend hours over the internet interacting with strangers who could pose as a th reat as it is easy to fake an identity over the internet. They would very much prefer using Facebook, Twitter or Tumblr etc. instead of studying or doing an outdoor activity. Therefore, this addiction can be very destructive. â€Å"A cross sectional study was carried out in Spain in 2003 to define mass media use in teenagers (television, mobile phones, computers, Internet and video games) and to examine its influence on teenagers health and development. The data collected was based on a sample of 884 teenagers between the ages of 14 and 18 years. The sample was retrieved from high schools residing in six towns in Cantabria (Spain). The results showed that all adolescents had a television at home and 24% of the families owned four or more TV sets. The presence of mass media in teenagers’ rooms was 52.5% for TV sets, 52% for the internet, 57.8% for computers, and 38.7% for gaming consoles. The most frequently found media in their bedrooms were cassette/radio players and compac t disks with percentages of 76.8 % and 67.4 %, respectively. Furthermore, teenagers spent on average 3 hours on television on weekdays and 3.2 on weekends. They spent 0.69 hours on average on weekdays and 1.09 hours on the weekend. On internet they spent on average 0.83 hours on the weekdays and 1.15 hours on the weekend. Other results of the study showed that about 87.2 % of the teenagers owned a cell phone. The average age at which they got their first phone was 13 years old. Almost half the teenagers (46.4 %) took their mobile phones to high school and reported that they had an average of three mobile phones at home. Also most of them (82.1 %) surfed the internet but boys preferred surfing and downloading games whereas girls preferred chatting and sending e-mails. Sixty-two percent of the teenagers had been to a cybercafà © and 40.8 % had visited a pornographic website, especially boys (33.1 % of boys versus 7.7 % of girls; p Mass media is a very powerful tool to influence the minds of anyone, let alone a teenager. Teenagers are in that stage of growing up where everything around them influences them. The way they talk, dress and act depends a lot on what they are exposed to. For example, if a teenager sees his or her favourite celebrity endorsing a product which may or may not be necessary, he or she may want to buy it regardless of how useful the product is. This is a strategy many big businesses use to their advantage as they can easily sell products, even if they are of bad quality. â€Å"Advertising is a very manipulative technique to promote products. Special attention needs to be paid to advertising’s effects. Three product categories are especially important for teens’ health: cigarettes, alcoholic beverages, and food. According to the teen marketing experts, adolescents â€Å"admit that advertising is a more important trend source than DJs, VJs, movies, celebrities, or the coolest and weirdest people at school† (P, 1995). We must be alert about the effects of advertising that deliberately exploit the insecurities of adolescents and attempt to â€Å"sell† them the answers to their problems with an abundance of new products. Television is a medium people widely now have easy access to. Nowadays, there are many shows such as Breaking Bad, Game of Thrones and Da Vinci’s Demons etc. on television that glorify sex, drugs, alcohol and violence. Online streaming and downloading has made it even more convenient to watch shows and films which means that teenagers have easier access to their favourite shows that contain obscenity. This kind of exposure poses as a threat as many teenagers find sex, drugs, alcohol, smoking and violence to be â€Å"cool†. As a result, many teenagers fall prey to problem of addiction. Drugs, alcohol, smoking and sex are all termed as things that are addictive and if one develops the problem of addiction, life becomes really hard to cope with. It’s like you are moving towards your own destruction. It must be quite a challenge for adolescents not to see portrayals of alcohol in their everyday use of the media. Alcohol appears in more than 70% of prime-time televisi on shows and in 90% of the movies† (Roberts DF, Henriksen L, Christenson PG, 1999). Greater than one third of all main characters drink alcohol, but fewer than 2% are shown as having a drinking problem (N, 1987). Advertising links alcohol with a variety of benefits that appeal to teenagers such as socializing, virility, sexual attraction, romance, escape, and adventure (Atkin CK, Strasberger VC, Comstock GA (eds), 1993), and few consequences (e.g., hangovers, accidents, violence, and embarrassment). Alcohol advertising also often represents slices of life that concentrate on the drinkers and the drinking occasions rather than on the qualities of the product itself, which may be particularly appealing to teens who are using the media for ideas about how to be in the world. Video games are vastly played by the teenagers of today. The video games are highly addictive as well contain a lot of mature content. In US about 97% of the teens play video games. The local video game industry over there brings in nearly a revenue of $12 billion a year. Many studies have shown that video games with violent content are associated with violent behavior. This concern is important because most of the popular video games contain violence. The increase in aggressive behavior is partly linked to the amount of time teens spend on playing video games. (Gentile Anderson, 2003) have stated that playing video games may increase aggressive behaviour because violent acts are frequently repeated throughout the video game. This process of repetition has long been considered as an effective teaching method in strengthening learning patterns. Another study carried out in 2008 took a nationally representative sample of 1,102 adolescents between the ages of 12 and 17 and their parents. From the results, it was found that 97 percent of the young respondents play video games. Further divided on the basis of gender, 99 percent of boys and 94 percent of girls played video games. Half the respondents had also played a video game the previous day. This emphasizes on how frequently they are exposed to video games. Even though most parents checked the censor’s rating before permitting their child to buy it, 50 percent of boys and 14 percent of girls preferred games with â€Å"Mature† (M) or Adult-only (AO) rating, which implies a high degree of exposure to obscenity. (Irvine, 2008) This preference is due to the impact of mass media. It is slowly becoming a norm that children are exposed to such stuff at such a tender when they are learning things that shape up their personality. This is why such exposure can be damagi ng. I know people who like go to parties, and smoke just because it is something everyone does or something that you casually see on television or in video games. Since media has the ability to manipulate people’s mind and attitudes, it also influences gender stereotypes. Advertising, news industries and entertainment, usually portray men and women with stereotypes, in which women and girls are likely to be placed in disadvantaged situations, for example passive and submissive roles. This happens a lot in third world countries e.g. Pakistan. Several TV shows and commercials show women usually playing the role of a housewife while men are shown to be more career-oriented, focusing on their occupations. As a consequence, traditional gender roles and power relations have been deeply imputed in people’s sub-consciousness through the mass media which limits the development of human personalities as well as social equality. When youngsters look at advertisements, TV shows or films, they are exposed to images of stereotypical representations. This stereotyping can be seen for all ages. For example, you can see little girls playing with Barbie Dolls and Teddy bears or having tea parties while boys are shown playing with action figures. Male teenagers are usually portrayed as sporty whereas female teenagers are shown as girls who have interest in fashion. Women are more often presented in commercials doing grocery because they are seen as responsible for making daily purchases. Men commonly advertise cigarettes, cars, business productsor investments, whilewomen are shown rather in the commercials with cosmetics, shoes, bags and clothing. Another important distinction is the face-ism phenomenon inthe advertisements, which refers to showing the entire figure in case of a woman and close-up shots in case of a man (Matthews, J.L, 2007). All of this indirectly injects the idea in the minds of the people that girls and boys should be educated differently. It is typical for girls to be tender and have concerns with being beautiful and popular, while boys are encouraged to be tough and consider more about their careers than appearance. Therefore, teenage boys and girls behave and reflect as the expectation of their society and culture instead of the way they really want. If we look at the other side of the argument which talks about mass media as a positive influence on teenagers we can see that mass media is the reason why communication is now so much easier and quicker than in the past. The internet is one of the most widely used mediums nowadays. With the help of social media apps such as Facebook, Twitter, WhatsApp etc. one can communicate with friends and family easily, especially those who live far away at a cheaper cost in comparison to making phone calls or travelling expenses. Mass media also keeps people up-to-date on events happening around the world within a short amount of time. For example, if a famous personality passed away; you will hear this immediately. Media keeps you informed. It also helps in other things like entertainment and gaining knowledge. Also Mass media is a good way to promote positive messages to teens. Since teens are immersed in media culture, it is wise to use that platform as a means to promote information and education about a variety of things that affect teenagers such as mental illnesses, sexually transmitted diseases, drug use or even suicide. â€Å"The More You Know† is an Emmy Award-winning series of Public Service Announcements(PSAs) which broadcasts on theNBCfamily of channels in the US and other locations. Even though not all of the messages given out are geared towards teens, many of these short, 90 minute commercials give messages that educate and inform teenagers of the possible consequences of certain behaviours.â€Å"The More You Know† has dealt with smoking, driving, suicide and even safe sex. Another good example is of Doves Real Beauty Campaign. With this campaign Dove has used their advertising for a greater good. Dove’s Real Beauty Campaigntargets self-esteem and has als o been selecting real women and girls in their campaigns rather than super thin models. They’ve also have taken a multi-media approach using an interactive website and in-person education to encourage girls, particularly to feel good about their bodies and appreciate themselves the way they are (Delp). Yes, media helps us cause awareness quite easily and the â€Å"The More You Know† and Dove’s Real Beauty Campaign are wonderful campaigns to raise awareness and help people with low-self-esteem but many teenagers are still widely exposed to ideal body types which are considered attractive therefore, it is hard to change their mind-set. It is important to be aware of mass media and the impact it has on teenagers, especially for parents, because they need to be aware of how it is affecting their child. If parents are more aware, they can be more understanding and helpful towards their children. The disadvantages are rather more important than the advantages because if one does not think about them then one will also not be able to come up with solutions and there can be severe consequences. Parents firstly need to realize that it is impossible to separate a teens life from media, especially in today’s world. However, parents can take the lead in restricting usage by spending more time with their teens and consistently discussing matters that are affecting mass media and teenagers. Parents should encourage their children for more outdoor activities as well limit the time their teenagers spend on the watching television and surfing the internet. Also since advertising is a very powerful tool, it could be used in a more positive way to put better influence on teenagers. Mass media has both negative and positive influences on teenagers as it can be seen from the points mentioned above. While I do not deny nor disregard the fact that mass media has indeed made lives easier, its negative influences still outweigh the positive ones in my opinion. As the famous saying goes, that everything is good in moderation. Therefore the extensive usage of mass media is now leading to more problems than the benefits it is providing us with. Bibliography Atkin CK, Strasberger VC, Comstock GA (eds). (1993). Effects of media alcohol messages on adolescent audiences. Adolescent Medicine: State of the Art Reviews, 527-541. Delp, V. (n.d.). Mass Media and Teenagers. Retrieved from Love To Know Teens: http://teens.lovetoknow.com/Mass_Media_and_Teenagers Gentile, D. A., Anderson, C. A. (2003). Violent video games: The newest media violence hazard. D. A. Gentile (Ed.), Media violence and children. Irvine, M. (2008, September 16). Survey: 97 Percent Of Children Play Video Games. Retrieved from The Huffington Post: http://www.huffingtonpost.com/2008/09/16/survey-97-percent-of-chil_n_126948.html Mass media consumption in adolescence. (2005). An Pediatr (Barc), 63, 516-525. Matthews, J.L. (2007). Hidden sexism: Facial prominence and its connections to gender and occupational status in popular print media. Sex Roles: A Journal of Research, 57, 515-525. N, S. (1987). Drinking, sex, and violence on television: The cultural indicators perspective. 17, 245-260. P, Z. (1995). Wise Up to Teens: Insights into Marketing and Advertising to Teenagers. Roberts DF, Henriksen L, Christenson PG. (1999). Substance use in popular movies and music. Zeiger, S. (n.d.). The Media Affects a Teens Body Image. Retrieved from Love to know teens: http://teens.lovetoknow.com/The_Effects_Media_Has_on_Teenagers_Body_Image

The Symbolic Role of Birds in Kate Chopins The Awakening Essay

The Symbolic Role of Birds in Kate Chopin's The Awakening The Awakening by Kate Chopin is a truly enlightening novel about a young woman who begins to really live her life for herself, breaking out of the various barriers of society and family. Chopin uses symbolism as an excellent tool to slip her ideas to readers, causing them to think, giving readers a glimpse into the life of this young woman at a time when women were harnessed by many restraints. The birds that appear throughout the novel are the most intriguing symbols; they are used many different ways, to mean many different things, and to portray various emotions and situations. As the novel begins, Chopin likens Edna to a bird in a gilded cage. Edna is not free, but that is okay because she has not yet begun to see what life has to offer; she has not yet begun to awaken. Through Edna's desire for Robert, she begins to realize that she is like the bird in the cage, not wanting for anything materially but still trapped. Edna cannot fly away to freedom; she is tied by social constraints and especially by he...

Anthrax and Bioterrorism :: Biological Terrorism Terrorist Homeland Security

Bioterrorism, in the last decade, has become a real threat to the world. Since the anthrax attacks on American soil in 2001, the world has become aware of the potential risk of an anthrax attack. Anthrax is the disease caused by the Bacillus anthracis bacteria. Ever since early history, anthrax has occurred in livestock animals and in humans. The bacteria prevent the macrophages from communicating with the rest of the body. Thus, the body cannot fend of anthrax and slowly organs begin to deteriorate. However, a series of antibiotics and vaccinations are available in case of an exposure to anthrax. Bacillus anthracis, or anthrax, has recently become a greatly feared pandemic. The breakout of anthrax on American soil in October of 2001 opened the world's eyes to the possibilities of bioterrorism of anthrax. Since then, government associations, such as the CDC and EPA, have taken precautions in case of another bioterrorist attack, particularly an anthrax attack. The history of anthrax dates back to biblical times in ancient Egypt (Anthrax Info 1). In 16th Century B.C., the Israelites were under the control of powerful Ramses II. According to Bible, a series of plagues fell upon Egypt in attempt to free the Israelites. One of these plagues involved the death of the cattle, sheep, and goats. Many historians believed the cause of death was due to anthrax inhalation. The first non-livestock case of anthrax occurred in the early 19th Century (Anthrax Info 4). After coming into contact with anthrax infected animals, many farmers were cutaneously inoculated with anthrax. This outbreak sparked the scientific research of anthrax. 2 Written documentation of anthrax began with Robert Koch's discovery of the bacteria that caused anthrax. Koch performed experiments that explained the attributes of anthrax. Using the spleens of anthrax infected animals, Koch inoculated mice (Elsevier 3). The mice later died and Koch concluded that anthrax could be transferred through the bloodstream. Koch also grew Bacillus anthracis in a culture to further his research. During the incubation process, Koch noticed that the bacteria formed spores when faced with a harsh environment (Elsevier 4). He later discovered that such spores could still cause the anthrax disease. Because of his revolutionary findings, Koch is credited with discovery of anthrax. Using Koch’s discoveries, 20th Century scientists began developing weaponized anthrax. Due to the spores’ durability, anthrax has been a very favorable biological weapon. The first incident of weaponized anthrax was recorded during the First World War.

David Emil Durkheim and the Social Causes of Suicide Essay -- Suicide

David Emil Durkheim is a renowned sociologist and also France’s first professor of sociology. Born on 15th, April in France, he successfully advocated for sociology to be recognized as an academic discipline. He did his first recognizable work titled ‘The division of labor in society’ in 1893 and then started the first European department sociology in a university in his homeland of France. David Durkheim's main concern was to try and understand how communities could maintain their integrity and coherence in the modern era where common religions and ethnic backgrounds were stumbling blocks. He went ahead and developed many other sociology theories and arguments until his death in 1917. Some of his famous published work includes social stratification, sociology of knowledge, deviance and religion. But one of the most outstanding and fascinating of his work is suicide which was published in 1897 (Calhoun, 2002). How Durkheim was able to show the social causes of suicide. Durkheim compares the suicide rates among different categories of people both in individual levels and in the community at large. He treats suicide as a social fact explaining its occurrence by the use of social facts like; lack of group attachment and lack of behavior regulation. In personal perspective he argued that suicide is a personal act that involves personal psychology and purely individual thoughts. His explanations on suicide were partly hindered by unavailability of very precise or complete statistical data. He went ahead and described suicide as caused by factors like climate, race, mental illness, hereditary and imitation (Sociology 250, 1999). Durkheim was able to show the social cause of suicide by observing and studying on varying socia... ...ciologytwynham/suicide-presentation-927179 Durkheim Emile. Emile Durkheim on suicide. Retrieved from: http://www2.uvawise.edu/pww8y/Soc/-Theorists/Durkheim/Suicide.html Eskenazi Karin, (2009). Largest ever study of suicide in the military. Retrieved from: http://www.medicalnewstoday.com/releases/157916.php Evans, (2011). Suicide causes and motivations. Retrieved from: http://www.crimescenecleanup.com/Suicide_Causes_and_Motivations.html Hassan Riaz, (1996). Social factors in suicide in Australia. Retrieved from: http://www.aic.gov.au/documents/4/9/0/%7B490EDFD9-212E-414F-B4E5-F3DA8A6D0413%7Dti52.pdf Kushner Howard I & Sterk Claire E, (2005). The limit of social capital. Retrieved from: http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1449331/ Sociology 250, (1999). Social facts and suicide. Retrieved from: http://uregina.ca/~gingrich/o26f99.htm

Cosmic Creations Myths Across Culture Essay

Many Christians have a very vague idea about the collection of the Old- Testament. The Old-Testament books are stories of the most famous myths. The Hebrew Bible (Old Testament) is a book of Hebrew text, assemble by Jewish scholars of the seventh to tenth centuries A. D. It also contains two stories of creation. In addition, the book of Genesis is known as the book of creation of humankind. The book is also believes to be written during the reign of King Solomon and known as possessing two authors. The first story of creation states that, â€Å"In the beginning God creates the heaven and the earth. Genesis 1:1 – 2:4, is the story of creation in six days and resting on the seventh. The emphasis of this story is the creation of order out of chaos. The second author speaks of the creator of humankind, â€Å"Yaweh. † This story focuses more on human temptation and punishment. The creator, Yahweh made the heavens and the earth. It is said that Yahweh took dust from the moist land and shapes it into the shape of man. He breathes the breath of life into man and he comes to life. Yahweh is the creator of all things from the Garden of Eden, to the rivers that flow from the four corners of the world. He is also the creator of the Garden of Eden, the tree of life, and the tree knowledge of good/evil. One day after watching man, he decides that man should have a help-mate. He causes man to fall into a deep sleep and remove one of his ribs, creating woman. The man was Adam (earth or clay) and the woman name was Eve (life). The myth goes on to state how Adam and Eve eats the apple from the tree of knowledge after the serpent deceives them. In addition, eating the apple opens their eyes to the knowledge of good and evil. They are then ban from the Garden of Eden. Yahweh curses the serpent, Adam, and Eve. He places a half-human, half-lion creature with wings at the gates to keep them out. The emphasis of this story, generally agrees to be the older story of the two, is on the development of the problem of evil and what its origins are. Another recognizes the division of the two accounts; the first gives details accountable for the whole creation whereas the second one is focuses on the creation of man. The world consists of many myths like the universal flood. The universal flood, from the book Genesis: Chapter six-eight, is a world- wide historical myth. The Book of Genesis, believe to be written by Moses, is an interesting myth. The Old-Testament states that the earths receives rain for 40 days and 40 night to exterminate all of mankind. Liberal Christians believe the legendary Noah’s flood is just a spiritual myth. However, the Conservative Christians, believe the book of Genesis was written by Moses under the inspiration of God. Interpretations of the ark, plays an important role in early Christian doctrine. They believe the worldwide flood happens just as Moses records it. That God gives Noah instructions for building the ark: it is to be of gopher wood with the inside and out with pitch. There were three decks, one door (in the side) and a window 18 inches high probably running around the top of the vessel under the roof. It was about 450-feet, long by 75-feet in beam, and 45- high. The creation of the ark is to protect those who would reproduce the earth. The supernatural myth is that all humans and animals will be extent, except for those who made it to safety on the ark: two or seven animals of each â€Å"kind,† and Noah, his wife, and family. The universal flood was the largest genocide in history, involving the extermination of all almost every man, woman, youth, child, infant, and newborn. Christians believe God intentionally triggers the physical processes that would lead to the extermination of all of the land animals and all but eight humans in the flood because of humanity’s sinful behavior. Typically liberal Christians of the Old-Testament, Noachian, Babylonian, and hundreds of other believe a myth. There are many links in some ways of the Old-Testament and the Babylonians historic flood. There is no source of sufficient water to produce a worldwide flood that covered the highest mountains. Even if it did happen, there is no place to which the flood waters could subside. Genesis was written over an interval of many centuries by at least five author/editors. The universal flood story was derives from an earlier Babylonian myth by two of these authors. The Genesis flood myth is obviously base on an earlier Babylonian myth; there are many correspondences between the two legends. The Babylonian myth appears as an earlier legend that in turn, bases memories of the Black Sea catastrophe. The â€Å"Epic of Creation,† of the Babylonian, also known as Enuma Elish, dates to the second millennium B. C. Before anything had a name there was Aspu (sweet water) and Tiamet (salt –water). With the creation between the two they begot Lahmu and Lahamu. With the joining of the gods create Ansha, Kishar, and Anu. As the creation proceeds through generations, there is creation of Ea and his brothers. Ea and his brothers cause disruptions and Aspu becomes furious. He plots with gods of the first generation to slew Ea and his brothers. However, Ea hears of the plot and kills Aspu first. Tiamet hearing of her husband death sends out an army of creatures she creates. She creates the Kingu, a leader for the creatures, to avenge Aspu death. Ea, however; has a plan of his own. The myth states that Ea and Damkina create Marduk (Assur) to defend divine beings from the attack of Tiamet, the ocean goddess. Marduk propositions the gods and ensures their safety only if he becomes their supreme leader and forever. The gods agree that he would be their leader even after the treats pass. After agreeing to the terms Marduk slew Tiamet by ripping her body into two halves. These two halves became the earth and the sky. After the death of Tiamet the gods and Marduk in agreement and the creation of Babylon begin. Marduk creates the planets, stars, coordinate the moon, sun, and the -whether. In addition, Marduk becomes the sun. He decides to relieve the gods of external labor by creating mankind. It is said he creates bones (from the monsters he slew), cover them with flesh and breaths the breath of life forever freeing gods work. In conclusion, many parallels with the Genesis, accounts for that some historians concluding that Genesis account was simply a rewriting of the Babylonian story. As a reaction, many who wants to maintain the uniqueness of the Bible, argues either that there is no real parallels between the two accounts or that the Genesis narratives are written first and the Babylonian myth copies the biblical account.

Copyright Law Case Study

Music Business Music Technology & Production Year 3 K00121700 Case Study Ronan Mitchell Abstract Copyright Law is an important entity within the music industry. It protects the owner of authorship from infringement. Infringement arises when the copyright owner’s work is used without their consent. Although sounds cannot be copyrighted, some cases have shown that the argument of copyrighting one’s voice can sometimes hold weight in a court of law. Singer Tom Waits sued snack manufacturer Frito Lay for hiring a singer to impersonate him in an advert.Mr. Waits felt that his artistic copyright had been infringed upon. Frito Lay’s defense argued that a voice cannot be protected by copyright law as it is a sound and not a musical piece of work. They referred to a similar case involving Bette Midler in which she sued Ford motors for using an impersonator in a commercial to imitate her voice. Although Midler lost the case, it created ambiguity over the issue of an artist ’s right their voice, if they believe it to be distinctive. Tom Waits, unlike Bette Midler, won the lawsuit and earned him $2. 6 million.This case served to highlight the complexities involved with advertising agencies using, not only an artist’s work, but also their identity. Introduction The music industry is notoriously rife with legal disputes. Many of these are due to infringement of copyright. A grey area arises, however, when it comes to advertising. In a lot of cases, an artist will gladly accept royalties and/or remuneration to have their song featured in an advertisement. But in certain instances, artists will have strong opinions about having their music feature in an advertisement.When this happens, advertising companies who use this artist’s work can find themselves in the middle of an ugly legal dispute. This case study endeavors to discuss some of the legal complexities involved when advertising companies use an artist’s musical work. Sever al cases exist in the United States where advertising agencies ran into legal disputes over music featured in an ad, even when not infringing upon standard copyright laws. I have chosen two cases to cross examine to highlight certain legal problems that certain advertising companies face.The first case examined for this study is Tom Waits Vs Frito-Lay, Inc. In this case Tom Waits sued the Frito-Lay snack manufacturer and their advertising agency for voice misappropriation and false endorsement. Despite not infringing on any copyright laws, Waits won the case and was awarded $2. 6 million in compensatory damages, punitive damages and attorney’s fees. (Roesler, 1992). The second case examined in this study will look at is Bette Midler Vs Ford Motor Co. This case, which preceded Waits lawsuit, is almost identical in that Ford’s advertising agency, Young & Rubicam, Inc. hired an unknown singer to impersonate Midler on a version of her track â€Å"Do You Want To Dance†. (Lurie, 1994) Midler took legal action and sued Ford for $10 million, also citing voice misappropriation. Unlike Tom Waits case, US District Judge A. Wallace Tashima ruled against Midler, stating that the evidence presented wasn’t sufficient and that a voice is not a copyrightable entity (Los Angeles Times, 1989) Study To better understand the legalities that face companies in these instances, we must first develop a better understanding of what copyright law entails. In short, Copyright is a property right.It is a set of laws and regulations set in place to protect to form of expression of ideas. The ideas themselves cannot be protected by such laws. The idea must take on some tangible form, such as a recorded piece of music, a produced film, piece of art, etc. The owners of these rights are protected by copyright law from anyone who would copy their work and reproduce it for their own monetary gain without the owner’s express permission. It is the owner of the co pyright who may authorize the use of their work by another party, but only they only reserve the right to do this at their discretion. Neff, 2012) Naturally, as there are many different mediums for expressing ideas, copyright law is divided into many different subsections. This is to cover all vessels for creative expression. On a simple scale, copyright subsists in four sections; Music, Film and Broadcast, Literary Publication and Original Databases. The music subset consists of Musical, Literary, Dramatic or Artistic Works. The musical copyright covers works of music that do not contain words. How notes are arranged to form melodies, song structures and chord progressions are protected by this copyright.Certain musical elements are not protected by this. If a guitarist has particularly unique guitar tone, he cannot have this protect by a copyright. A specific tone is not a tangible musical work and therefore cannot be protected. However, if the same guitarist recorded an original piece of music with that guitar tone, this recording is now a tangible body of work and can be protected by musical copyright. It is the music itself that is protected. Not the sound. (Neff, 2012) This is a particularly interesting element of Tom Waits lawsuit against Frito-Lay.The defendants argued that the â€Å"voice misappropriation† case was invalid as one cannot own the rights to certain style of singing. (UMKC School of Law, n. d. ) Tom Waits is an American singer, songwriter, composer and actor. Almost as much for his music, he is renowned for his unique gravelly, guttural singing voice. His voice has been described as sounding like â€Å"like it was soaked in a vat of bourbon, left hanging in the smokehouse for a few months, and then taken outside and run over with a car. † (Graff, G & Durchholz, D 1998).Tracy-Locke, Frito Lay’s advertising agent, approached Tom Waits about using is his song â€Å"Step Right Up† in an advert for RioSalsa Doritos. They put together a version of the song which featured new lyrics relevant to the product and played this for Waits. Tom Waits refused outright as he is vehemently opposed using his music to sell products. It was interesting that they chose that particular song, as the lyrics are a satirical indictment of advertising. The song features advertising slogans used sarcastically to describe a product that supposedly does everything from â€Å"shine your car† to â€Å"make you six foot five, blonde and beautiful†. Jacobs, 2000) When he refused, the Tracy-Locke company then hired a singer to impersonate Tom Waits style of sing over a song that bared a lot of similarities the Waits â€Å"Step Right Up†. Tom Waits took legal action and sued for voice misappropriation and false endorsement. (Roesler, 1992) As the lyrics for the song were altered to suit the ad, Waits literary copyright was unaffected. The literary copyright pertains to a work of words which are written, spoken or sung. This work does not specifically need to be written down for the copyright to apply. A recording of such work holds he same right as literary work that is written or printed. Written musical notation also falls under this subsection regardless if it is written down, printed or recorded. (Neff, 2012) As for the musical rights to the song, it transpired that Tom Waits, despite having written the piece, did not have authorship of the copyright for â€Å"Step Right Up†. In normal circumstances, authorship of the copyright to a sound recording is held by the produce of said recording. In this case, the authorship fell to Fifth Floor Music run by Herb, Martin and Evan Cohen.Frito Lay had in fact obtained the synchronisation license from Fifth Floor Music. This licence enabled them to reproduce a new song extremely similar, albeit not identical, to â€Å"Step Right Up† to which the new jingle lyrics were added. Tom Waits was unaware of this so was unable to ste p in and terminate the dealings. Although, having no authorship of the copyright, it is questionable as to whether or not this would have had any sway in the proceedings at all. (Jacobs, 2000) Similarly, in Bette Midler’s case, like Waits, Midler was not the owner of the copyright.She did not write the song nor did she pen the lyrics. Ford Co. bought the rights the song â€Å"Do You Want To Dance† from the publishing company that had ownership over the copyright. This meant that Ford had no obligation to contact Bette Midler with regards to their intentions to use the song for their commercial. (Lurie, 1994) Since Midler had no ownership rights, the defense argued that her â€Å"voice misappropriation† was preempted by the copyright act. However, this was rejected as they found that copyright cannot be preempted if the subject matter â€Å"does not come within the subject matter of copyright†¦.. ncluding works or authorship not fixed in any tangible medium of expression. † (UMKC School of Law, n. d. ) It was decided that, since it was not possible to copyright a particular sound (like that of the guitar tone), the voice was not suitable copyright subject matter. Thus, copyright preemption did not apply. (UMKC School of Law, n. d. ) Although the court ruled in favor of the defendant, Midler’s case of â€Å"voice misappropriation† raised the question of a celebrity’s right to control over their identity, with respect to commercial use. This ambiguity was vital to the outcome of Waits lawsuit only three years later. Lurie, 1994) The copyright preemption issue in Midler’s case was referred to in Waits Vs Frito Lay. The defense requested that, since Tom Waits was not the lawful owner of the music copyright, the preemption of copyright law did not apply in this instance as it had with Midler. Waits case was not for infringement of a tangible copyrightable piece of work, but for infringement of voice. Again , voices are merely sounds; and sounds are not protected by copyright law. (UMKC School of Law, n. d. ) Despite this, the defense argued that, even though they had copied Waits musical style, they did not imitate his voice.This was found to be untrue, however. It transpired that Tracy-Locke’s executive producer was quite concerned with the legal implications of their singer’s striking similarity to Waits’ voice. He requested that they record another version of the jingle asking the singer to sing less like Waits. Unhappy with the result, Frito Lay insisted they use first version. (UMKC School of Law, n. d. ) On the day that the commercial was due to air, Tracy Locke’s managing vice president spoke with their attorney regarding what legal issues they might encounter.He was advised that there was a strong possibility of legal ramification due to recent case law that recognized a distinctive voice as protectable. However, as style was not protectable, their attorney informed them that the case might hold no merit. (UMKC School of Law, n. d. ) Despite the warning, Frito Lay chose the version that imitated Tom Waits’ distinctive voice. It was proposed that the jury be given a proposed instruction on the distinction between voice and style which read, â€Å"In contemporary music, there are a great many styles or â€Å"sounds,†Ã¢â‚¬ ¦Ã¢â‚¬ ¦ Style is not subject to ownership.No singer can appropriate for himself any style and exclude others from performing in the same style. Any singer is free to sing in the same style. † (UMKC School of Law, n. d. ) This instruction was rejected by the district court. Given that there were a lot of similarities between this case and Midler’s â€Å"voice-misappropriation† case, the jury was asked to decide whether or not they found Waits’ style to be distinctive. The defense argued that the omitted instruction was an error in judgment as this then left the jury unc lear as to what the distinction was between voice and style. (UMKC School of Law, n. d. Waits argued that although no copyright infringement had occurred, he felt his artistic integrity had been compromised. It was put forth that anyone had heard the advertisement would automatically assume that it was Waits singing. Waits has strongly spoken out about artists taking money to allow their music to be used to sell product. He felt that, as the Doritos advertisement jingle sounded identical to his voice and musical style, that his fans would assume he participated in the advertisement and had willing endorsed the product. This, he asserted, was damaging to his reputation and his career as an artist. UMKC School of Law, n. d. ) The jury then listened to several of Tom Waits songs to determine both his musical and vocal style. The court then played them the Doritos advertisement in question for comparison. To convince them further, Waits attorneys had them hear testimonies from people wh o had in fact thought that it was Waits in the advertisement. (Roesler, 1992) This argument was persuasive enough to sway the jury. They were convinced when they heard to advertisement and the testimonies that, despite the fact that no copyrightable material had been infringed upon, Waits’ artistic integrity had been compromised.The jury found that the defendants had â€Å"acted with oppression, fraud or malice† (Roesler, 1992, p. 15). Tom Waits was awarded 2. 6 million dollars in compensatory damages and attorney’s fees. Conclusion In conclusion, we can see from the above cases that copyright is a bastion for musical artists. They help to protect an artist’s right to their work and a right to their form of expression from being exploited by large companies and advertising agencies who can sometimes try to profit from their work.Although, as they are vital to protecting an artist’s creative work, we can also seen from the cases studied that they ca n protect much more than that. Technically, in the eyes of the law, only a tangible body of work can by protected by these rights. However, as this study has shown, in certain rare cases, these rights can be manipulated to encompass, not only an artist’s work, but their identity, persona and artistic integrity when exploited.As made evident by the unusual Tom Waits lawsuit, it seems that advertising companies in particular must wade carefully when wishing to use unlicensed music for commercials. As their sole intention is for making money, they can be looked at very callously by court jury. Thus, certain unscrupulous can land in a lot of trouble despite not infringing on a copyrighted piece of work. Although situations such as this are quite unusual, they highlight the importance of copyright law within the music industry. References Graff, G & Durchholz, D 1998, Musichound Rock: The Essential Album Guide. Visible Ink, Detroit * Jacobs, J. A 2000, â€Å"Copyright: Tom waits Vs Frito Lay†, viewed 04 January 2013, < www. tomwaitsfan. com/tom%20waits%20library/www. tomwaitslibrary. com/copyright-fritolay. html> * Los Angeles Times (1989), Bette Midler Loses Ford Sound-Alike Lawsuit : Celebrity: $10-million suit over TV car commercial is dismissed but action against the ad agency is allowed to stand, viewed 06 January 2013, http://articles. atimes. com/1989-10-27/business/fi-901_1_bette-midler * Lurie, K. (1994) Waits v. Frito-Lay: The Song Remains the Same.. Cardozo Arts & Ent. LJ, 13, 187. , Available at: http://heinonline. org/HOL/LandingPage? collection=journals&handle=hein. journals/caelj13&div=26&id=&page= [Accessed: 6th January 2013]. * Neff, F. 2012, â€Å"Copyright and Related Rights Act 2000; Introduction to Copyright Overview And Originality in Copyright†, * Neff, F. 012, â€Å"Authorship and Ownership of Copyright; Copyright and Related Acts 2000 Sections 21 to 23†, * Roesler, M. (1992) Waits v. Frito Lay,. 978 F. 2d 1093 (9 th Cir. 1992), Available at: http://www. markroesler. com/pdf/caselaw/Waits%20v. %20Frito-Lay%20Inc. %20_1992_. pdf [Accessed: 6th January 2013] * University of Missouri Kanas City School of Law (1992) Waits v. Frito Lay, Inc. United States Court Of Appeals For The Ninth Circuit, Available at: http://law2. umkc. edu/faculty/projects/ftrials/communications/waits. html [Accessed: 4th January 2013].