Screening of Non Target Compounds in Wastewater Samples

Screening of Non Target Compounds in Wastewater Samples Report Since October 2012, I have worked in a special project about Elimination of pharmaceuticals and organic compounds: Development of concepts and novel, cheap cleaning procedures – Formation of metabolites by ozonoation. It was a kind of training for me and a special key for my PhD work. We are interested in screening of non target compounds in wastewater samples. Wastewater samples are collected from different wastewater treatment plants at different treatment points. For example: before ozonation, after ozonation and after biological treatment steps. These compounds are extracted by solid phase extraction (SPE) method using certain solid material (OASIS HLB). This kind of SPE is suitable to extract hydrophilic and lipophilic analytes. We did several steps to extract those compounds using different procedures and different analyzing tools. We used HPLC-UV, LC-MS and GC-MS to analyze the extracted compounds. The toxicological tests are achieved for each sample in order to discove r the efficiency of wastewater treatment and the effect of treatment to obtain new unknown transformation products. In this project, I learned so many things like: How to validate and develop a method to extract polar and non polar compounds from wastewater matrixes using certain SPE steps. How to choose the best solid phase materials to extract a wide range polarity of chemical compounds in wastewater matrixes. Getting the principles for handling of different analytical instruments to validate specific methods and to analyze the extracted compounds. Taking enough time to review the statistical principles which are necessary to find the optimum ways for treatment. Achieving the possibilities to analyze the output data and comparing different procedures to find out the best one for analysis. Combining chemistry with biology in order to evaluate the toxicological estimates and to know the best wastewater treatment step. Now, I am working on developing a method to extract the following six compounds from water matrix: Catechol, trans,trans-Muconic acid, p-Benzoquinone, 1H-Benzotriazole, p-Nitrophenol and 2,6-Dichloraniline. Catechol, trans,trans-Muconic acid and p-Benzoquinone are transformation products generated after treatment of the parent compound (Bisphenol A) with ozone in aqueous solution (water). Bisphenol A (BPA) belongs to the numerous anthropogenic compounds considered as endocrine disruptors. Although less estrogenic toward aquatic organisms than natural hormones, BPA has been reported to be able to induce feminization phenomena in various species of animals. BPA is commonly used for the production of polycarbonate plastics and epoxy resins. It is also used as stabilizer or antioxidant for many types of plastics such as polyvinyl chloride (PVC). BPA is detected with a high frequency in surface waters. 1H-Benzotriazole has been found in wastewater and the subsequently impacted surface water. This compound is employed to prevent metal corrosion and as UV-inhibitors, and found to use in applications such as airplane deicing fluids, dishwashing detergents, and plastic formulations. p-Nitrophenol is degradation product generated throughout the ozonation process of the antibiotic sulfamethoxazole. Sulfamethoxazole in combination with trimethoprim is used to treat a wide range of human diseases, such as urinary and respiratory tract infections. There are many publications that have reported about the presence of this antibiotic drug in sewage treatment plants, hospital effluents and rivers. Besides, this compound might be expected to be present in groundwater, because the antibiotic sulfamethoxazole is also applied to animals as growth promoter. 2,6-Dichloraniline is a metabolite produced after ozonational step of the drug diclofenac in aqueous solution. Diclofenac is one of the most commonly used pain killers. It is used to treat painful conditions such as arthritis, sprains and strains, gout, migraine, dental pain, and pain after surgical operations. There are many articles that have reported about the presence of this drug in sewage treatment plants. First step, I prepared different standard solutions for each compound, then validated and developed a method to analyze these compounds by using HPLC-UV instrument. A mixture of methanol and water (pH=2) are used at certain progress time and different ratios to obtain the best LC chromatogram with good separation and resolution for each compound in the mixture. The maximum wavelength (ÃŽ ») for each compound is known by using UV-spectrophotometer. Table (1) summarizes the information obtained after analyzing my target compounds by HPLC-UV. Table 1 Substance Retention time tR (min) ÃŽ » (nm) Catechol (1) 26.35 278 t,t-Muconic acid (2) 28.43 278 p-Benzoquinone (3) 30.46 278 1H-Benzotriazole (4) 34.42 278 p-Nitrophenol (5) 39.89 228 2,6-Dichloraniline (6) 48.04 228 Figure (1) shows the HPLC-UV chromatogram (relative response in mV vs. tR) for a mixture of six compounds in one prepared stock solution. 5 6 Figure 1 2 4 1 3 In order to develop a method to analyze the target compounds; the limit of detection (LOD) and limit of quantification (LOQ) should be calculated in order to know the sensitivity of HPLC-UV instrument towards each compound. The LOD value for each compound was calculated from a chromatogram on the basis of signal-to-noise (S/N) ratio of 3. The LOQ value for each compound was calculated from a chromatogram on the basis of signal-to-noise (S/N) ratio of 10. Table (2) shows the values of LOD and LOQ for each compound. Table 2 Substance LOD (ng/L) LOQ (ng/L) Catechol (1) 8.8 29.3 t,t-Muconic acid (2) 1.2 4.0 p-Benzoquinone (3) 6.3 21.0 1H-Benzotriazole (4) 8.5 28.3 p-Nitrophenol (5) 27.4 91.3 2,6-Dichloraniline (6) 18.0 60.0 For linearity and statistical evaluation, I prepared mixture solutions of six compounds at concentrations of 0.1, 0.25, 0.4, 0.55, 0.7, 0.85 and 1.0 mg/L. Table (3) shows the statistical data for the prepared stock solution of 0.7 mg/L. Table 3 Substance % Relative response Correlation coefficient (r) Catechol (1) 100 0.999 t,t-Muconic acid (2) 101 0.999 p-Benzoquinone (3) 106 0.999 1H-Benzotriazole (4) 100 0.999 p-Nitrophenol (5) 100 0.999 2,6-Dichloraniline (6) 104 0.999 The linearity at my working range is shown as follows: Now I am working in developing a preparation method to extract these compounds from water matrix by using different solid phase materials. Up to now, I tried two types of solid phase cartridges: OASIS HLB and SPEED DISK cartridges. It’s noticed that OASIS HLB gave higher recovery than SPEED DISK. In order to find out the best solid phase material, I will try many types of SPE. After finishing this step, I will develop a method to extract and analyze about 30 chosen chemical compounds which are produced after the ozonation process of pharmaceutical and parent compounds in water matrix. These compounds will be: Diclofenac, 2,6-Dichloroaniline, Metoprolol, Sulfamethoxazole, 4-nitrophenol, Bisphenol A, Catechol, trans,trans-Muconic acid, cis,cis-Muconic acid, p-Benzoquinone, Ciprofloxacin, Paracetamol, 1,2,4-Benzenetriol, Oxalic acid, Succinic acid, Malic acid, Malonic acid, Oxaloacetic acid, Hydroquinone, Maleic acid, EDTA, Glyoxylic acid, Formaldehyde, Carbamazepine, Glyoxylic acid, Oxamic acid and 1H-Benzotriazole.

Master Tag Case

The key benefit to the revised approach is that the tags are being sent directly to the customer that needs them, the growers. The growers are then able to order another batch of tags once the plants have grown if they have a surplus in plants. Thus the reasoning for the revised approach is fulfilled by not having an abundance of un needed tags being shipped to the grower from the seed companies.The pros of the revised approach is the seeds will be planted with the tags and the tag wont leave the seed all the way from plantation until it reaches the retail customer. Also, if the grower is able to clone plants they would have the accessibility of ordering any new tags directly from MasterTag. The pro for the seed company is that they don’t have to sort tags to send off their order to the growers.Another pro is the seed companies wont have a surplus of tags in their warehouse, however, if the plant doesn’t survive from the growth of the seed the grower may build up a surp lus of tags. Although still, the grower would be better to utilize the process of order from MasterTag because they would know what plants survived from the seed. The cons of the plan is that it adds an extra step to the Growers manufacturing process. They now have to do forecasting and planning with two companies MasterTag and the seed companies, rather than just with the seed companies.

Ventria Bioscience and the Controversy over Plant-Made Medicines

Case Study: â€Å"Ventria Bioscience and the Controversy over Plant – Made Medicines† GB590 Corporate Social Responsibility Prof. Timothy Loney By Willette Marchany Rivera February 22, 2011 Introduction: Case overview Ventria Bioscience, a biotechnology firm based in California, faces the challenge of commercializing a product with potential and considerable public health benefits. Ventria had developed a ground-breaking technology using genetically modified (GM) rice to grow the proteins lactoferrin and lysozyme, both found in human breast milk, which can be used for the treatment of diarrhea in children, tourists and the military. Lawrence and Weber, 2010, p. 494) However, the pioneer biotechnology invention has to go through regulatory processes and stakeholder’s scrutiny, before it can enter the market. There are ethical concerns over the plant-based medicines and opposition coming from consumer advocates, environmentalists, rice farmers and food safety activ ists. Ventria needs to overcome the regulatory environment and manage its stakeholder relations in order to succeed and release this product for sale. In order to do so they must establish a strategic plan to improve their triple bottom line performance.They need to convince stakeholders that the potential benefits are desirable and that they can safely and responsibly deliver the product to be commercialized. Even then, Ventria and the biotechnology industry might always face opposition from groups against genetically modified organisms in which human genes are also manipulated. â€Å"The public’s reactions to plant- made pharmaceuticals were likely to be extreme, given the high benefits, potential risks, and deep moral quandaries posed by these new technologies. † (Lawrence & Weber, 2010, p. 92) Financial goal Ventria’s financial goal is to make profit from producing in a big scale the GM rice they developed and selling it at an affordable price. The plant-mad e pharmaceutical concept was created in order to take advantage of the capability of harvesting the proteins in a natural host instead of using a costly laboratory environment where manufacturing would be slower and in a smaller scale. Ventria’s financial goal seems to be intertwined to the capability of producing the GM rice outdoors over a large amount of land.Environmentalists and rice farmers are highly concerned with the possibility of comingling happening and the adverse impact on the ecosystem this could have. Other than that, the Union of Concerned Scientists, a policy advocacy group, warned that it is unwise to produce drugs in plants outdoors, because there would be little control over the doses people might get exposed to, and some might be allergic to the proteins. (Grace, 2011, para. 24-25) Environmentalists are concerned too about Ventria using acres of arable land to harvest medicine instead. (Grace, 2011, para. 0) Social goal Ventria’s social goal shoul d be to contribute to the treatment of diarrhea in children, the military and tourists at an affordable price with their innovative plant-made pharmaceutical without damaging society. In order to do so, they shall get the local and global public to trust the biotechnology industry and plant-made pharmaceuticals. They also need to assure that the product or its production will not harm or negatively affect human lives. The GM rice cannot get mixed with or contact in any way crops designated for human food supply.At the same time, consumers need to be informed honestly about the content of the products and that they are GM. Otherwise, customers would be deceived. There are ethical concerns about the use of human genes in this GM rice and consumer rights to be informed should be placed first. Food safety is also an issue as this GM rice remains to be widely tested in humans and be approved by the FDA. The company also needs to become liable in case the GM rice contaminates other rice f armers’ crops and contaminated products are sent to the human food supply.Environmental goal Ventria’s environmental goal would be to produce the GM rice without contaminating the environment or throwing off the natural balance, that is, without disturbing the ecosystem. They cannot allow comingling to happen. Also, they need to avoid and control the risks of any adverse impact of the GM rice to the ecosystem by taking measures to avoid potential harms to the wildlife and the spreading of the GM rice crops that could lead to undesirable hybrids.Summary: Triple bottom line performance and strategic recommendations After considering all the financial, social and environmental factors that adversely affect their performance, Ventria is in position of making a strategic decision. They should consider first to modify or radically change their production strategy and second to enter in a marketing process focused in educating the public about their product. These strategies can help them achieve their three bottom-line goals. They need to provide a safer way of producing their product and obtain the permits and the approval to sell it.Their financial, social and environmental goals can only be attained by focusing in resolving the issues with their stakeholders. There are two recommendations on how to change their current production strategy. They can search for an isolated area of arable land away from other rice farmers and set stringent measures of control to avoid the risk of contaminating other crops. However, controlling all the risk factors in an open crop field would be complicated and it is uncertain to which degree it could be accomplished.Another option would be to consider production in greenhouses. This would be probably more costly, but will ensure a higher degree of control. Finally, Ventria would have to ensure the safety of their product and take on an honest advertising campaign to disseminate doubts and concerns about their invention . Likely, there will be opposition based on the ethical concerns about GM. However, public campaigns that provide straight forward and clear information from the developers will give customers more tools to make an informed decision about the product.References Grace. (2011, February 2). Genetically modified rice now on its way to fields in several  countries. Nwoandsecretsocieties. WordPress. com. Retrieved February 24, 2011 from http://nwoandsecretsocieties. wordpress. com/2011/02/02/genetically-modified-rice-now-on-its-way-to-fields-in-several-countries/ Lawrence, A. T. (2010). Ventria Bioscience and the Controversy over Plant- Made Medicines. In Lawrence, A. T. , Weber J. , Business and Society: Stakeholders, Ethics,

Jingle Bells in Spanish

Here are three Spanish-language Christmas songs that can be sung to the tune of Jingle Bells. Though none of them attempt to be a translation of the English song, they all borrow the bell theme. Following each song is an English translation, and at the bottom of the page is a vocabulary guide for the boldfaced words. Cascabel Cascabel, cascabel,mà ºsica de amor.Dulces horas, gratas horas,Juventud en flor.Cascabel, cascabel,tan sentimental.No ceces, oh cascabel,de repiquetear. Translation of Cascabel Jingle bell, jingle bell,music of love.Sweet time, pleasant time,Youth in bloom.Jingle bell, jingle bell,So sentimental.Dont stop, oh jingle bell,the happy ringing. Navidad, Navidad Navidad, Navidad, hoy es Navidad.Con campanas este dà ­a hay que festejar.Navidad, Navidad, porque ya nacià ³ayer noche, Nochebuena, el nià ±ito Dios. Translation of Navidad, Navidad Christmas, Christmas, today is Christmas.It is necessary to celebrate this with bells.Christmas, Christmas, because just last nightthe little baby God was born. Cascabeles Caminando en trineo, cantando por los campos,Volando por la nieve, radiantes de amor,Repican las campanas, brillantes de alegrà ­a.Paseando y cantando se alegra el corazà ³n,  ¡ay! Cascabeles, cascabeles, tra la la la la. ¡Quà © alegrà ­a todo el dà ­a, que felicidad, ay!Cascabeles, cascabeles, tra la la la la.Que alegrà ­a todo el dà ­a, que felicidad Translation of Cascabeles Traveling by sleigh, singing through the fields,Flying through the snow, beaming with love,The bells ring, brilliant with joy.The heart is cheerful as it strolls along and sings. Whee! Jingle bells, jingle bells, tra-la-la-la-la.What joy all day, what happiness! Whee!Jingle bells, jingle bells, tra-la-la-la-la.What joy all day, what happiness! Translation Notes In this context, a cascabel typically refers to a small metallic ball with a piece of metal inside that is designed to make a ringing sound when the ball is shaken. Such a ball is often attached to the collar of a pet or the harness of a horse so its motion can be heard. A cascabel can also be a baby rattle or the rattler of a rattlesnake.Note how dulces (sweet) and gratas (pleasant or agreeable) are placed before the nouns they modify. This is commonly done with adjectives that have an emotional aspect. Thus, dulce after a noun might refer to sweetness as a taste, while dulce in front may refer to a persons feelings about the noun.The suffix -tud is added to a slightly modified root word, joven (meaning young), to turn the adjective into a noun, forming juventud.  Tan is closely related to tanto; both are used in making comparisons.Cesar is a cognate of to cease. Just as we would be more likely to use stop rather than cease in everyday English speech, so would Spanish speakers mor e likely use parar or terminar. Note how this song uses the familiar second-person form ceses, speaking to the cascabel as if it were a person. This is an example of personification.Repiquetear usually refers to the lively ringing of bells, although it can also be used to the sound of drums or a repeated pounding on something.Navidad is the word for Christmas as a noun, while navideà ±o is the adjectival form.Campana usually refers to a traditional bell or something that is in the shape of one.Hay que followed by an infinitive is a common way of saying that something needs to be done.Festejar usually means to celebrate, although celebrar is more common. Normally, the event being celebrated (este dà ­a) would be placed after festejar, as would be done in English. Presumably, atypical word order was used here for poetic purposes.Either và ­spera de Navidad or Nochebuena can be used to refer to Christmas Eve.Ya is a vaguely defined adverb used to add emphasis. Its translation is hig hly dependent on context.Ways of referring to last night in addition to ayer noche include anoche, ayer por la noche, and la noche pasada.Nià ±ito is an example of a diminutive noun. The suffix -ito has been appended to nià ±o (boy) to make it refer to a baby boy.Dios is the word for God. As with the English god, the word is capitalized when it is used as the name of a specific divine creature, especially the Judeo-Christian God.Campo usually means field. In the plural, as here, it can refer to an undeveloped rural area.Ay is a multipurpose exclamation that usually has a negative connotation such as ouch! Here it seems to be more of a simple shout of joy.Dà ­a, the word for day, is one of most common nouns ending in a that is masculine, breaking a common gender rule.