APPLIED ENVIRONMENTAL CHEMISTRY 5MARKS: 1)Environmental chemistry Environmental chemistry is the scientific study of the chemical and biochemical phenomena that occur in natural places. It should not be confused with green chemistry, which seeks to reduce potential pollution at its source. It can be defined as the study of the sources, reactions, transport, effects, and fates of chemical species in the air, soil, and water environments; and the effect of human activity on these. Environmental chemistry is an interdisciplinary science that includes atmospheric, aquatic and soil chemistry, as well as heavily relying on analytical chemistry and being related to environmental and other areas of science. Environmental chemistry involves first understanding how the uncontaminated environment works, which chemicals in what concentrations are present naturally, and with what effects. Without this it would be impossible to accurately study the effects humans have on the environment through the release of chemicals. Environmental chemists draw on a range of concepts from chemistry and various environmental sciences to assist in their study of what is happening to a chemical species in the environment. Important general concepts from chemistry include understanding chemical reactions and equations, solutions, units, sampling, and analytical techniques. Contamination A contaminant is a substance present in nature at a level higher than typical levels or that would not otherwise be there.[2][3] This may be due to human activity. The term contaminant is often used interchangeably with pollutant, which is a substance that has a detrimental impact on the surrounding environment.[4][5] Whilst a contaminant is sometimes defined as a substance present in the environment as a result of human activity, but without harmful effects, it is sometimes the case that toxic or harmful effects from contamination only become apparent at a later date. The "medium" (e.g. soil) or organism (e.g. fish) affected by the pollutant or contaminant is called a receptor, whilst a sink is a chemical medium or species that retains and interacts with the pollutant. Environmental indicators Chemical measures of water quality include dissolved oxygen (DO), chemical oxygen demand (COD), biochemical oxygen demand (BOD), total dissolved solids (TDS), pH, nutrients nitrates and phosphorus), heavy metals (including copper, zinc, cadmium, lead and mercury), and pesticides. Applications Environmental chemistry is used by the Environment Agency (in England and Wales), the Environmental Protection Agency (in the United States) the Association of Public Analysts, and other environmental agencies and research bodies around the world to detect and identify the nature and source of pollutants. These can include: Heavy metal contamination of land by industry. These can then be transported into water bodies and be taken up by living organisms. Nutrients leaching from agricultural land into water courses, which can lead to algal blooms and eutrophication.[7] Urban runoff of pollutants washing off impervious surfaces (roads, parking lots, and rooftops) during rain storms. Typical pollutants include gasoline, motor oil and other hydrocarbon compounds, metals, nutrients and sediment (soil).[8] 2)Types of Reactions: Combustion A combustion reaction is when all substances in a compound are combined with oxygen, which then produces carbon dioxide and water. Combustion is commonly called burning. It is an exothermic reaction, which means heat is produced and is easily distinguished. Combustion occurs predominantly in automobiles, homes, and in factories. An example of a combustion reaction is as follows: CxHy + O2 --> CO2 + H2O Synthesis A synthesis reaction is when there is a combination of two or more substances and a compound results. An example of a synthesis reaction is as follows: A + B --> AB Decomposition Decomposition is the opposite of synthesis. It is when a compound is broken down into simpler substances, usually through electrolysis. An example of decomposition is as follows: AB --> A + B Dissociation Dissociation is commonly mistaken as decomposition, but there is a difference. When the compound is broken down, it is broken down into ions rather than atoms, so there will be a charge on the product side of the equation. An example of dissociation is as follows: AB --> A+ + BSingle Replacement Reactions In a single replacement reaction, there is a rule that is always followed. A metal replaces a metal, or a nonmetal replaces a nonmetal. An example of a single replacement reaction is as follows: A + BC --> AC + B Double Replacement Reactions In a double replacement reaction, this rule is always followed. A metal replaces a metal, and a nonmetal replaces a nonmetal. An example of a double replacement reaction is as follows: AB + XY --> AY + XB 3)Definition and measurement pH pH is defined as minus the decimal logarithm of the hydrogen ion activity, aH+, in a solution. This definition was adopted because ion-selective electrodes, which are used to measure pH, respond to activity. Ideally, electrode potential, E, follows the Nernst equation, which, for the hydrogen ion can be written as where E is a measured potential, E0 is the standard electrode potential, R is the gas constant, T is the temperature in kelvins, F is the Faraday constant. For H+ number of electrons transferred is one. It follows that electrode potential is proportional to pH when pH is defined in terms of activity. Precise measurement of pH is presented in International Standard ISO 31-8 as follows:[7] A galvanic cell is set up to measure the electromotive force (e.m.f.) between a reference electrode and an electrode sensitive to the hydrogen ion activity when they are both immersed in the same aqueous solution. The reference electrode may be a silver chloride electrode or a calomel electrode. The hydrogen-ion selective electrode is a standard hydrogen electrode. Reference electrode | concentrated solution of KCl || test solution | H2 | Pt Firstly, the cell is filled with a solution of known hydrogen ion activity and the emf, ES, is measured. Then the emf, EX, of the same cell containing the solution of unknown pH is measured. The difference between the two measured emf values is proportional to pH. This method of calibration avoids the need to know the standard electrode potential. The proportionality constant, 1/z is ideally equal slope". to the "Nerstian The pH scale is logarithmic and therefore pH is a dimensionless quantity. p[H] This was the original definition of Sørensen,[4] which was superseded in favor of pH in 1924. However, it is possible to measure the concentration of hydrogen ions directly, if the electrode is calibrated in terms of hydrogen ion concentrations. One way to do this, which has been used extensively, is to titrate a solution of known concentration of a strong acid with a solution of known concentration of strong alkali in the presence of a relatively high concentration of background electrolyte. Since the concentrations of acid and alkali are known, it is easy to calculate the concentration of hydrogen ions so that the measured potential can be correlated with concentrations. The calibration is usually carried out using a Gran plot.[8] The calibration yields a value for the standard electrode potential, E0, and a slope factor, f, so that the Nernst equation in the form can be used to derive hydrogen ion concentrations from experimental measurements of E. The slope factor, f, is usually slightly less than one. A slope factor of less than 0.95 indicates that the electrode is not functioning correctly. The presence of background electrolyte ensures that the hydrogen ion activity coefficient is effectively constant during the titration. As it is constant, its value can be set to one by defining the standard state as being the solution containing the background electrolyte. Thus, the effect of using this procedure is to make activity equal to the numerical value of concentration. The difference between p[H] and pH is quite small. It has been stated[9] that pH = p[H] + 0.04. It is common practice to use the term "pH" for both types of measurement. pH in nature pH-dependent plant pigments that can be used as pH indicators occur in many plants, including hibiscus, red cabbage (anthocyanin) and red wine. The juice of citrus fruits is acidic because of the presence of citric acid. Other carboxylic acids occur in many living systems. For example, lactic acid is produced by muscle activity. The state of protonation of phosphate derivatives, such as ATP is pHdependent. The functioning of the oxygen-transport enzyme hemoglobin is affected by pH in a process known as the Root effect. 20MARKS: 1)Calculations of Ph The calculation of the pH of a solution containing acids and/or bases is an example of a chemical speciation calculation, that is, a mathematical procedure for calculating the concentrations of all chemical species that are present in the solution. The complexity of the procedure depends on the nature of the solution. For strong acids and bases no calculations are necessary except in extreme situations. The pH of a solution containing a weak acid requires the solution of a quadratic equation. The pH of a solution containing a weak base may require the solution of a cubic equation. The general case requires the solution of a set of non-linear simultaneous equations. A complicating factor is that water itself is a weak acid and a weak base. It dissociates according to the equilibrium 2H2O H3O+(aq) + OH-(aq) with a dissociation constant, Kw defined as Kw = [H+][OH-] where [H+] stands for the concentration of the aquated hydronium ion and [OH-] represents the concentration of the hydroxide ion. Kw has a value of about 10-14 at 25°C, so pure water has a pH of about 7. This equilibrium needs to be taken into account at high pH and when the solute concentration is extremely low. Strong acids and bases Strong acids and bases are compounds that, for practical purposes, are completely dissociated in water. Under normal circumstances this means that the concentration of hydrogen ions in acidic solution can be taken to be equal to the concentration of the acid. The pH is then equal to minus the logarithm of the concentration value. Hydrochloric acid (HCl) is an example of a strong acid. The pH of a 0.01M solution of HCl, is equal to −log10(0.01), that is, pH = 2. Sodium hydroxide, NaOH, is an example of a strong base. The p[OH] value of a 0.01M solution of NaOH, is equal to −log10(0.01), that is, p[OH] = 2. From the definition of p[OH] above, this means that the pH is equal to about 12. For solutions of sodium hydroxide at higher concentrations the self-ionization equilibrium must be taken into account. Self-ionization must also be considered when concentrations are extremely low. Consider, for example, a solution of hydrochloric acid at a concentration of 5×10−8M. The simple procedure given above would suggest that it has a pH of 7.3. This is clearly wrong as an acid solution should have a pH of less than 7. Treating the system as a mixture of hydrochloric acid and the amphoteric substance water, a pH of 6.89 results. Weak acids and bases A weak acid or the conjugate acid of a weak base can be treated using the same formalism. Acid: HA Base: HA+ H+ + AH+ + A First, and acid dissociation constant is defined as follows. Electrical charges are omitted from subsequent equations for the sake of generality and its values is assumed to have been determined by experiment. This being so, there are three unknown concentrations, [HA], [H+] and [A-]] to determine by calculation. Two additional equations are needed. One way to provide them is to apply the law of mass conservation in terms if the two "reagents" H and A. CA = [A] + [HA] CH = [H] + [HA] C stands for analytical concentration. In some texts one mass balance equation is replaced by an equation of charge balance. This is satisfactory for simple cases like this one, but is more difficult to apply to more complicated cases as those below. Together with the equation defining Ka, there are now three equations in three unknowns. When an acid is dissolved in water CA = CH = Ca, the concentration of the acid, so [A] = [H]. After some further algebraic manipulation an equation in the hydrogen ion concentration may be obtained. [H]2 + Ka[H] - Ka Ca = 0 Solution of this quadratic equation gives the hydrogen ion concentration and hence p[H] or, more loosely, pH. This procedure is illustrated in an ICE table which can also be used to calculate the pH when some additional (strong) acid or alkali has been added to the system, that is, when CA ≠ CH. For example, what is the pH of a 0.01M solution of benzoic acid, pKa = 4.19? Step 1: Ka = 10-4.19 = 6.46×10−5 Step 2: Set up the quadratic equation. H]2 + 6.46×10−5[H] - 6.46×10−7 = 0 Step 3: Solve the quadratic equation. [H+] = 7.74×10-4; pH = 3.11 For alkaline solutions an additional term is added to the mass-balance equation for hydrogen. Since addition of hydroxide reduces the hydrogen ion concentration, and the hydroxide ion concentration is constrained by the selfionization equilibrium to be equal to Kw/[H+] CH = [H] + [HA] -Kw / [H] In this case the resulting equation in [H] is a cubic equation. General method Some systems, such as with polyprotic acids, are amenable to spreadsheet calculations.[22] With three or more reagents or when many complexes are formed with general formulae such as ApBqHr the following general method can be used to calculate the pH of a solution. For example, with three reagents, each equilibrium is characterized by and equilibrium constant, β. [ApBqHr] =βpqr[A]p[B]q[H]R Next, write down the mass-balance equations for each reagent CA = [A] + Σp βpqr[A]p[B]q[H]r CB = [B] + Σq βpqr[A]p[B]q[H]r CH = [H] + Σr βpqr[A]p[B]q[H]r - Kw[H]-1 Note that there are no approximations involved in these equations, except that each stability constant is defined as a quotient of concentrations, not activities. Much more complicated expressions are required if activities are to be used. There are 3 non-linear simultaneous equations in the three unknowns, [A], [B] and [H]. Because the equations are non-linear, and because concentrations may range over many powers of 10, the solution of these equations is not straightforward. However, many computer programs are available which can be used to perform these calculations; for details see chemical equilibrium#computer programs. There may be more than three reagents. The calculation of hydrogen ion concentrations, using this formalism, is a key element in the determination of equilibrium constants by potentiometric titration. 2)Branches: The branches of microbiology can be classified into pure and applied sciences.[16] Microbiology can be also classified based on taxonomy, in the cases of bacteriology, mycology, protozoology, and phycology. There is considerable overlap between the specific branches of microbiology with each other and with other disciplines. Pure microbiology Taxonomic arrangement Bacteriology: The study of bacteria. Mycology: The study of fungi. Protozoology: The study of protozoa. Phycology (or algology): The study of algae. Parasitology: The study of parasites. Immunology: The study of the immune system. Virology: The study of the viruses. Nematology:The study of the nematodes Integrative arrangement Microbial cytology: The study of microscopic and submicroscopic details of microorganisms. Microbial physiology: The study of how the microbial cell functions biochemically. Includes the study of microbial growth, microbial metabolism and microbial cell structure. Microbial ecology: The relationship between microorganisms and their environment. Microbial genetics: The study of how genes are organized and regulated in microbes in relation to their cellular functions. Closely related to the field of molecular biology. Cellular microbiology: A discipline bridging microbiology and cell biology. Evolutionary microbiology: The study of the evolution of microbes. This field can be subdivided into: Microbial taxonomy: The naming and classification of microorganisms. Microbial systematics: The study of the diversity and genetic relationship of microorganisms. Generation microbiology: The study of those microorganisms that have the same characters as their parents. Systems microbiology: A discipline bridging systems biology and microbiology. Molecular microbiology: The study of the molecular principles of the physiological processes in microorganisms. Other Nano microbiology: The study of those microorganisms on nano level. Exo microbiology (or Astro microbiology): The study of microorganisms in outer space. Weapon microbiology: The study of those microorganisms which are using in weapon industries. Applied microbiology Medical microbiology: The study of the pathogenic microbes and the role of microbes in human illness. Includes the study of microbial pathogenesis and epidemiology and is related to the study of disease pathology and immunology. Pharmaceutical microbiology: The study of microorganisms that are related to the production of antibiotics, enzymes, vitamins,vaccines, and other pharmaceutical products and that cause pharmaceutical contamination and spoil. Industrial microbiology: The exploitation of microbes for use in industrial processes. Examples include industrial fermentation and wastewater treatment. Closely linked to the biotechnology industry. This field also includes brewing, an important application of microbiology. Microbial biotechnology: The manipulation of microorganisms at the genetic and molecular level to generate useful products. Food microbiology and Dairy microbiology: The study of microorganisms causing food spoilage and foodborne illness. Using microorganisms to produce foods, for example by fermentation. Agricultural microbiology: The study of agriculturally relevant microorganisms. This field can be further classified into the following: Plant microbiology and Plant pathology: The study of the interactions between microorganisms and plants and plant pathogens. Soil microbiology: The study of those microorganisms that are found in soil. Veterinary microbiology: The study of the role in microbes in veterinary medicine or animal taxonomy. Environmental microbiology: The study of the function and diversity of microbes in their natural environments. This involves the characterization of key bacterial habitats such as the rhizosphere and phyllosphere, soil and groundwater ecosystems, open oceans or extreme environments (extremophiles). This field includes other branches of microbiology such as: o Microbial ecology o Microbially-mediated nutrient cycling o Geomicrobiology o Microbial diversity o Bioremediation Water microbiology (or Aquatic microbiology): The study of those microorganisms that are found in water. Aeromicrobiology (or Air microbiology): The study of airborne microorganisms. Epidemiology: The study of the incidence, spread, and control of disease. 3) Environmental microbiology: Environmental microbiology is the study of the composition and physiology of microbial communities in the environment.[1][2][3] The environment in this case means the soil, water, air and sediments covering the planet and can also include the animals and plants that inhabit these areas. Environmental microbiology also includes the study of microorganisms that exist in artificial environments such as bioreactors. This field of microbiology was started as a result of experiments led by Martinus Beijerinck and Sergi Winogradsky. Microbial life is amazingly diverse and microorganisms literally cover the planet. Biodegradation of pollutants Microbial biodegradation of pollutants plays a pivotal role in the bioremediation of contaminated soil and groundwater sites. Such pollutants include chloroethenes, steroids, organophosphorus compounds, alkanes, PAHs and PCBs. Oil biodegradation Petroleum oil is toxic, and pollution of the environment by oil causes major ecological concern. Oil spills of coastal regions and the open sea are poorly containable and mitigation is difficult; much of the oil can, however, be eliminated by the hydrocarbon-degrading activities of microbial communities, in particular the hydrocarbonoclastic bacteria (HCB). These organisms can help remedy the ecological damage caused by oil pollution of marine habitats. HCB also have potential biotechnological applications in the areas of bioplastics and biocatalysis. Environmental genomics of cyanobacteria The application of molecular biology and genomics to environmental microbiology has led to the discovery of a huge complexity in natural communities of microbes. Diversity surveying, community fingerprinting and functional interrogation of natural populations have become common, enabled by a range of molecular and bioinformatics techniques. Recent studies on the ecology of cyanobacteria have covered many habitats and have demonstrated that cyanobacterial communities tend to be habitat-specific and that much genetic diversity is concealed among morphologically simple types. Molecular, bioinformatics, physiological and geochemical techniques have combined in the study of natural communities of these bacteria. Corynebacteria Corynebacteria are a diverse group Gram-positive bacteria found in a range of different ecological niches such as soil, vegetables, sewage, skin, and cheese smear. Some, such as Corynebacterium diphtheriae, are important pathogens while others, such as Corynebacterium glutamicum, are of immense industrial importance. C. glutamicum is one of the biotechnologically most important bacterial species with an annual production of more than two million tons of amino acids, mainly L-glutamate and L-lysine. Legionella Legionella is common in many environments, with at least 50 species and 70 serogroups identified. Legionella is commonly found in aquatic habitats where its ability to survive and to multiply within different protozoa equips the bacterium to be transmissible and pathogenic to humans. Archaea Originally, Archaea were once thought of as extremophiles existing only in hostile environments but have since been found in all habitats and may contribute up to 20% of total biomass. Archaea are particularly common in the oceans, and the archaea in plankton may be one of the most abundant groups of organisms on the planet. Archaea are subdivided into four phyla of which two, the Crenarchaeota and the Euryarchaeota, are most intensively studied. Lactobacillus Lactobacillus species are found in the environment mainly associated with plant material. They are also found in the gastrointestinal tract of humans, where they are symbiotic and make up a portion of the gut flora. Aspergillus Aspergillus spores are common components of aerosols where they drift on air currents, dispersing themselves both short and long distances depending on environmental conditions. When the spores come in contact with a solid or liquid surface, they are deposited and if conditions of moisture are right, they germinate. The ability to disperse globally in air currents and to grow almost anywhere when appropriate food and water are available means that ubiquitous is among the most common adjectives used to describe these moulds.[15] Microbial nitrogen cycling Microorganisms that convert gaseous nitrogen (N2) to a form suitable for use by living organisms are pivotal for life on earth. This process is called nitrogen fixation. Another set of microbial reactions utilise the bioavailable nitrogen creating N2 and completing the cycle in a process called denitrification. This crucial nutrient cycle has long been the subject of extensive research. Rhizobia Symbiotic nitrogen fixation is a mutualistic process in which bacteria reside inside plants and reduce atmospheric nitrogen to ammonia. This ammonia can then be used by the plant for the synthesis of proteins and other nitrogen-containing compounds such as nucleic acids. The Gram-negative soil bacteria that carry out this process are collectively referred to as rhizobia (from the Greek words Riza = Root and Bios = Life). 4)Colorimetry: Colorimetry is "the science and technology used to quantify and describe physically the human color perception."[1] It is similar to spectrophotometry, but is distinguished by its interest in reducing spectra to the physical correlates of color perception, most often the CIE 1931 XYZ color space tristimulus values and related quantities. Instruments Colorimetric equipment is similar to that used in spectrophotometry. Some related equipment is also mentioned for completeness. A tristimulus colorimeter measures the tristimulus values of a color.[3] A spectroradiometer measures the absolute spectral radiance (intensity) or irradiance of a light source.[4] A spectrophotometer measures the spectral reflectance, transmittance, or relative irradiance of a color sample.[4][5] A spectrocolorimeter is a spectrophotometer that can calculate tristimulus values. A densitometer measures the degree of light passing through or reflected by a subject.[3] A color temperature meter measures the color temperature of an incident illuminant. Tristimulus colorimeter In digital imaging, colorimeters are tristimulus devices used for color calibration. Accurate color profiles ensure consistency throughout the imaging workflow, from acquisition to output. Spectroradiometer, Spectrophotometer, Spectrocolorimeter The absolute spectral power distribution of a light source can be measured with a spectroradiometer, which works by optically collecting the light, then passing it through a monochromator before reading it in narrow bands of wavelength. Reflected color can be measured using a spectrophotometer (also called spectroreflectometer or reflectometer), which takes measurements in the visible region (and a little beyond) of a given color sample. If the custom of taking readings at 10 nanometer increments is followed, the visible light range of 400700 nm will yield 31 readings. These readings are typically used to draw the sample's spectral reflectance curve (how much it reflects, as a function of wavelength)—the most accurate data that can be provided regarding its characteristics. CRT phosphors The readings by themselves are typically not as useful as their tristimulus values, which can be converted into chromaticity co-ordinates and manipulated through color space transformations. For this purpose, a spectrocolorimeter may be used. A spectrocolorimeter is simply a spectrophotometer that can estimate tristimulus values by numerical integration (of the color matching functions' inner product with the illuminant's spectral power distribution).[5] One benefit of spectrocolorimeters over tristimulus colorimeters is that they do not have optical filters, which are subject to manufacturing variance, and have a fixed spectral transmittance curve—until they age.[6] On the other hand, tristimulus colorimeters are purpose-built, cheaper, and easier to use. The CIE recommends using measurement intervals under 5 nm, even for smooth spectra.[4] Sparser measurements fail to accurately characterize spiky emission spectra, such as that of the red phosphor of a CRT display, depicted aside.