Greetings esteemed ladies and gentlemen. I am currently researching and finishing up my research proposal for my biology/history senior composition (a required bachelor's thesis), which will be a year long project starting this semester till late March of next semester. I just finished my research proposal, and I am looking and asking fellow scientists in here to read my proposal and give me any hints and recommendations on things either it be in spelling, in methodology, in terminology, in citation etc. Please please guys, i need as much recommendation as possible. This is merely the proposal, which is the basis of my research--i dont actually begin laboratory and coring analysis until around october-november. By which, i will be spending most of my time in the lab or in the library or in the historical references on the development of the lake. I greatly appreciate any recommendations, i reiterate gain, to anything. I dont care if it is positive or negative, give it to me. I need input. An early thank you to everyone who helps out!!!
Here is my proposal essay:
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Historiographic Analysis of Sandy Lake and Eutrophication during the Turn of the
20TH Century: N:P ratios and Metals Identification
A. Lorenzo Lucino Jr.
September 21, 2007
Introduction:
The status of lakes throughout the world has been substantially affected by the onslaught of invasive human activity that has resulted in eutrophication of freshwater habitats, particularly lakes and ponds (Cole, 1983; Burgis and Troughton, 1987; Brock, 47). Numerous studies have procured that the specific limiting nutrients in eutrophic lakes throughout the world are the high levels of Phosphorus and Nitrogen that are given off from the sewage effluents of erected human housings, agricultural wastes from fertilizers, industrial wastes and increased water runoff by the effects of deforestation, atmospheric pollution and groundwater infiltration (Cole, 1977; Apelin et al, 1996; Markham, 1994; Schindler 1977; McMartin, 1994).
Nutrient loading of Phosphorus and Nitrogen in specific lakes and ponds have been quite disastrous for owners in that such occurrence results in the increase of macrophytes and other planktonic organisms such as dinoflagellates or commonly know as Cyanophyta, which are dominant in Phosphorus limited areas; some species of Nostacales, which has nitrogen fixing capabilities, become dominant if reduced Nitrogen becomes a limiting factor (Sommer, 1989).
One other effect of increased nutrient loading in lakes that are flanked by increased human activity is the degradation in water quality by an increase in algal biomass, discoloration and floating debris, which become an aesthetic problem for summer resorts that depend much on lake clarity( Becker and Neitzel, 1989; Cole, 1983). Additionally, eutrophic freshwaters with persistent algal biomass and debris become a health hazard for people whose living depends on a particular water body (Flemer, 1972; Hsiang-Te and Long-Gen, 1991); this will eventually lead to restrictions on water use such as drinking water, fish kills and odor. Another indicator of eutrophication in a freshwater habitat would be the Secchi disk visibility of particular lakes (Brock, 1985, Schindler, 1980; Smith, 1982); in clean and pristine lakes that are termed oligotrophic, Secchi disk visibility is high due to the considerable low algal biomass; however in eutrophic lakes where there is a considerable increase in algal biomass, the Secchi disk visibility is significantly lower than that of oligotrophic lakes. Thus an excessive eutrophication problem in a particular resort with limited recreational space becomes a financial problem (Schindler, 1978; Schindler 1977).
These specific indicators are effective in deducing whether or not a particular freshwater habitat is eutrophic or oligotrophic. Considering the fact that Phosphorus is critical for the growth of algal biomass and that varying Nitrogen levels are responsible for the presence of nitrogen fixing taxa; these two limiting factors are pivotal for understanding the eutrophication processes of lakes and other freshwater habitats. The comprehension of the paleolimnology of freshwater habitats is essential in that one can analyze the Phosphorus to Nitrogen levels during the primordial epoch before the advent of human invasive presence and compare those with levels during the era of human colonization and industrialization (Aplin et al, 1996). The collection of these data provides a better understanding of how industrialization and human activity in different regions of the globe affects the surrounding freshwater habitat via eutrophication. Other effects of industrialization that will be studied is the metallic sediments given off by coal emissions by coal plants. One in particular that will be studied was the coal plant that released its emissions in Sandy Lake, Pennsylvania. Proper analysis of paleolimnology will link eutrophication of Sandy Lake during the late 19th century and early 20th century to coal metal emissions.
Background Information:
The problems that come with the advent of heavy human colonization near lake areas and the rise of industrialization has been a contributing factor to the quality of lakes in the world (Markham, 1994). Ranging from the classical 18th century Great Industrial Revolution in Europe and later reverberating the same scheme in newly formed independent states in North America, Asia, Latin America and Africa (Hood and Porro, 2002; Magoc, 2006).
To fully understand the magnamity of the situation, it’s necessary to analyze the situation prior to the arrival of man in certain fresh water habitats, particularly in North America (Burgis and Morris, 1987). In one analysis of the paleolimnologic implications Linsley Pond and surrounding water beds in New England was that after the retreat of Pleistocene ice, these lakes were primarily oligotrophic for a short time before its phase towards eutrophy. This particular stage in the two lakes persisted in dynamic equilibrium for a millennia or so. However when one compares Linsley Lake with Potato Lake in Arizona, the main difference would be Potato Lake’s response to ameliorating climate in depositing organic oozes typical of eutrophy. In some data (Cole, 1975; Cole 1983), there was an increase in 60% ignition loss, yet a sudden decline in organic percentage; which correlates with the increased erosion of the drainage basin’s inorganic content in response to human agriculture and logging activities (Cole, 1975).
One thing that both Potato Lake and Linsley Pond both share, despite their geographic distance was that there was for a time, a long period of equilibrium in lake water. The nutrients entering the then undisturbed lakes received from yearly runoffs; which correlates with constant annual production and the bottom deposit’s constant accumulation, showcasing an example of trophic equilibrium (Cole, 1975), which reflects the status of the entire edaphic-climatic-morphologic system (Welch, 1992).
Changes in the trophic levels of these two specific lakes occurred right after the arrival and the establishment of European settlers in North America. Such activities that can be accountable for these changes would be forest cutting, agriculture; such disturbance resulted in increased nutrient input in the lakes. Studies also showed that even in Arizona, the loss of natural shrubby cover, called chaparral, to grass resulted in edaphic nutrient erosion, in particular nitrate, to the surrounding freshwater watershed. This of course is an effect of mass human agriculture (Howarth et al, 1988).
Such examples of increased nutrient loading and the historical reasoning for such Phosphorus and Nitrogen increase is universal as the same occurrence happened in Japan starting in the Meiji Restoration epoch, which occurred in the late 19th century after the deposition of the last Tokugawa Shogunate and the rise of the Imperial Privy Council as well as the immediate industrial revolution that took hold of Japan during its industrialization (Apelin et al, 1996). Such consequences of excessive human development and industrialization has been quite observed in other states in Asia that industrialized quite immediately after independency such as the People’s Republic of China, South Korea, the Philippines, The Federation of Malaysia, Indonesia, Vietnam, and India . Other regions of the world that experienced the same effects as those observed in North American as well as European industrialization were the states of South Africa, New Zealand, Australia, Liberia, Israel, Brazil, Mexico and Chile to name a few (Hood and Porro, 2002).
Specific examples of how industrialization and excessive human activities have resulted in increased nutrient loading such as Nitrogen and Phosphorus levels in fresh water bodies and thus titillated eutrophy is seen in Australia’s Lake Burragorang. What happened in the lake was that there was a great fire near the Blue Mountains in 1968 and showed that there was increased Phosphorus being washed into the reservoir, which was responsible for algal blooms, which then tainted and affected water supplies for the surrounding community around the lake (Aplin et al, 1996). Metallic substance can also be determined in its contribution to eutrophication by use of core analysis.
Additionally, there has been other problem in Australia pertaining to agricultural and pastoral use, which has observed in the state of New South Wales in which large amounts of fertilizers that were used on crops reached streams and lakes, where it aids in eutrophication. In one specific example, a toxic blue green algae bloom of cyanobacteria, caused by high amounts of phosphorus, polluted over 1000km of the Darling River in New South Wales (Aplin et al, 1996). Another example of eutrophication via industrial, commercial and agricultural use would be in Shanghai’s Dianshan Lake, which is a major drinking water source as well as subsistence supplier of fish for the people in that region. Due to the heavy deforestation around Dianshan Lake during the 1970s as well as the heavy industrialization occurring now, there has been an observable increase in Phosphorus levels in the lake, which greatly contributed to the eutrophication of Dianshan Lake (Hsiang-Te and Long-Gen, 1991).
The Nature of Phosphorus and Nitrogen:
Phosphorus is critical to all life, as it is universally observed in ATP processes (Adenosine triphosphate)as carrier of energy and the fact that nucleotides have phosphate groups and thus illustrates how nucleic acids as well as all living things’ need for phosphorus. Phosphorus is also a scarce element as compared to other principal atoms within living organisms such as carbon, hydrogen, oxygen, nitrogen and sulfur. An example of Phosphorus’ (Cole, 1978; Cole 1983) indicative nature in bringing life within freshwater habitat via the eutrophication process is how the turnover rates reflect the amount of phosphate in comparison to algal demand. However, due to increased human activity, the nature of Phosphorus has resulted in ‘over enrichment’ of lakes so to say via the process of Eutrophication, which occurs when sewage and other pollutants associated with human industrialization and activity bring excess amount of phosphorus back to the lakes, thus adversely increasing algal growth, and deoxygenating the fresh water region directly.
Nitrogen is yet another important factor that is indicative of eutrophication in that its presence is correlated with high percentages of nitrogen fixing bacteria such as Rhizobium (Cole, 1983), which are able to use nitrogenase, which reduces nitrogen into an ammonium ion, which then is then used by photosynthetic primary producers. Studies have recorded that O. rubescens are pivotal in foretelling whether or not a freshwater habitat is going through eutrophication, because the species of nitrogen limited and does not appear in lakes until Nitrogen content does arise (Cole 1983; Smith, 1982).
Significance and Project Statement:
The advent of industrialization in the third world as well as in the growth of human development in modernized states has led to increased waste deposits and industrial effluents in what was once trophically equilibrium lakes and influencing the culture of eutrophy (Stoermer and Smol, 1999; Magoc, 2006; Cooke et al, 1983). The increase deposits of Phosphorus and Nitrogen has resulted in growth of photsynethic algae, increase macrophytes, as well as the odor, and overall unaesthetic nature of a eutrophic lake. The presence of nitrogen (nitrate/nitrite) and phosphorus in the lakes will directly explain the presence of nitrogen fixing bacteria as well as phosphorus limited algae. The sampling of water from different lakes will allow testing for phosphorus and nitrogen; the collection of these data provides a better understanding of how human activity in this region of Northwestern Pennsylvania has affected the freshwater habitat via eutrophication and thus allows state environmental agencies to understand what limiting factors are in Lakes Pleasant as well as Conneaut and apply appropriate procedure to alleviate it.
Methods:
So far the best analysis of NO3-N in the water is to reduce nitrate in alkaline buffered solution to nitrite by having the sample go through a column of copperized cadmium metal fillings. The measurement of nitrite is observed by use of diazotization method that will eventually lead to a stable pink azo dye with an absorbance up to about 500µg NO3-N or NO2-N/liter. Concentrations of nitrite can be obtained prior to reduction of NO3 to NO2 via the diazotization technique. The cadmium reduction method will need glass columns for effective analysis; this method will allow analysis of about eight samples per hour per column.
To begin the analysis of the Nitrogen levels of a particular eutrophic lake, one would first need to prepare duplicate aliquots of nitrate standards to yield 50 ml from each Cd-Cu reduction column. The concentrations used should approximate those of the samples to be analyzed and should have lower and higher concentrations. Then take 50 ml of distilled water, nitrate standards, and samples into graduated cylinders; then add 5 ml of buffer solution and then thoroughly mix. Afterwards, add 10 ml of the buffered sample to the column and then discard the effluent. Finish adding the remaining buffered solution to the column in the cylinder and collect the 2 ml of effluent in the same cylinder, rinse the walls and then shake the cylinder. Afterwards collecting 25 ml of the column effluent, making sure to carry a water blank and a standard solution for each column used. Immediately, add about .5 ml of the sulfanilamide solution to the 25 ml sample of effluent from the column and then mix for 5-8 minutes, afterwards then add in 0.5ml of the naphthyl ethylenediamine solution and mix immediately. Allow the mixture to sit between 10 minutes to 2 hours; afterwards then measure the extinction coefficient at wavelength of 543 nm of the solution in a 1 cm cell. Use distilled water as a reference. If the extinction coefficient is more than 1.2 then dilute it by one half with distilled water and then remeasure. If the samples of the water have a visible coloration, a sample blank without the addition of naphthyl ethylenediamine reagent will be processed and obtain the extinction values of the absorbance of distilled water plus reagents (the blank), the absorbance of samples without naphthyl ethylenediamine reagent (if brown coloration) and the absorbance of standards or samples plus reagents. Afterwards, then prepare a standard curve of OD vs concentration for the corrected standards (ODcorr = ODs –ODb). The sample concentrations can then be read directly from the graph; if the standard curve is linear, as it should be, the concentration samples can be calculated by a unit extinction factor (F):
F= Standard concentration (ug NO3 – N/liter)
ODs of standard – ODb
Afterwards, then use: ug NO3 –N/liter = F[ODs of sample – (ODb + ODo)]
Then determine the reduction efficiency of the Cd-Cu columns by determining the extinction coefficient of a 100 ug NO3-N/ liter standard and a 100 ug NO2-N/liter standard. If the efficiency is not greater than 95%, the columns should be repacked. The nitrogen measured by Cd-Cu reduction technique is a combination of NO3-N and NO2-N in the sample. The NO2-N concentrations of the samples must be determined separately without the reduction procedure, as outlined in the next section, and subtracted from the NO3-N + NO2-N values determined.
Given: p = NO3-N + NO2-N concentrations
q = NO2-N concentration
r = efficiency of reduction column, %
Then ug NO3-N/ liter = p-(100/r)q.
To store the columns, pass about 100 ml of distilled water through the columns, followed by 50 ml of the ammonium chloride buffer solution. Leave the columns stored covered with the solution and cover tightly. To analyze the nitrite nitrogen, duplicate the aliquots of multiple nitrite standards with concentrations of the samples to be analyzed. Then take 50 ml samples of distilled water standards, blank s and samples into graduated cylinders and add about 5.0 ml of ammonium chloride buffer and mix. After 5 minutes of mixing, carefully add 1.0 ml of naphthyl ethylenediamine solution and mix. Allow to sit for 1 hour and after wards, compare the extinction of the solution against distilled water of 543 nm. Then path the lengths of 1 cm, 5cm, and 10 cm for nitrite concentrations of 60-300, 30-60 and 0-30 ug NO2-N/liter, respectively. Use the following calculation:
F= Standard concentration (ug NO3 – N/liter)
ODs of standard – ODb
Afterwards, then use: ug NO3 –N/liter = F[ODs of sample – (ODb + ODo)]
The analysis of Phosphorus comes next, particular concentrations of greater than 10 ug PO4-P/liter will go as follows: obtain water samples of 100 ml and heat to between 15 and 30 degrees Celsius. Properly make sure to measure the absorbance of a sample to obtain turbidity correction. Afterwards, add 10-15 ml of the composite reagent from a 25 ml graduated cylinder and mix thoroughly. Afte 1 hour, measure the extinction coefficient of the solution in a 1 to 10 cm cell at a wavelength of 885 nm. Then recalibrate the photometer to zero using distilled water before measuring the extinction coefficient of the sample. Then measure the absorbance of a reagent blank (ODb). Afterwards, subtract the extinction number of the reagent blank and the turbidity-color correction from the value for sample extinction to obtain a corrected sample extinction. Use the following equation: ODcorr = ODs – (ODb + ODturb).
Then prepare a standard curve by finding the absorbance of for standard solutions, which are diluted from the stock solution. The unit extinction factor (F) for PO4-P can be calculated as:
F = Standard concentration (ug PO4-P/liter)
ODstd- ODb
And: ug PO4-P/liter = F [ODs-(ODB + ODturb)]
For concentrations less than 10 ug PO4-P/liter, double the sample size and extract the blue complex with an organic solvent. Samples of .25 ml should be stored (as discussed earlier). Pipet 200 ml of water sample into a 250 ml separatory funnel (remember to keep the temperature between 15 to 30 degrees Celsius) and add about 20 ml of the composite reagent; mix thoroughly. To calculate total phosphorus levels, one has to make sure that there will be reagents, the same ones used for inorganic phosphate analyses. Persulfate solution, which is mixed 5% w/v K2S2O8 in distilled water. Add 16 l of the 5% Persulfate solution to 100 ml samples in 250 ml borosilicate flasks. Then place flasks in a boiling water bath for one hour (or autoclave for one-half hour at 1055 g/cm^2. Allow to cool and then adjust the volume to 120 ml. The liberated PO4-P is analyzed according to the methods used for inorganic P04-P (use procedures for concentrations < 10 ug P04-P/liter). The P04-P standards and reagent blanks will then be placed in identical boiling and volume adjustment procedures. Proceed with computation of a standard curve and calculations of sample concentrations.
To collect metal samples given off by coal during the turn of the 20th century, one would apply the following: Metal samples will be taken by core and metal samples will be digested for analysis with an aqua regia solution (2:1 Seastar nitric acid and hydrochloric acid) and headted to 70 degs C for 8-10 hours. After digestion, Teflon filters will be removed and the sample will be centrifuged to separate undigested material from the metal in the solution. The sample will be split into glass and Teflon vials for analysis of key metals: mercury, arsenic (glass), cadmium, lead and zinc and stored at 4 degs C. All metals samples will be analyzed via ICP-MS ELEMENT (magnetic sector-inductively coupled plasma-mass spectrometer). Cd, Pb, and Zn should be determined with a standard liquid sample introduction system. Isolation of the said metals are indicative of effects of eutrophication and biota during the specific period.
Begin historical research of Sandy Lake---?
Timeline
-October/November: Go to Lake Conneaut and Lake Pleasant and take water samples.
-November/December: Take additional samples of water and properly label each
-December: Begin analysis for Nitrogen (nitrite/nitrate)
-December/Jan: Begin analysis for Phosphorus (varying levels; greater or less than ug PO3-P/liter)
-February: Metal samples and isolation; data data data
-Feb: Present data to Professor Ostrofsky
-October-March: Begin historical/archive research or Conneaut and Pleasant Lake in Erie County Historical Society and/or Crawford County Historical Society
-Dec-March: Begin Writing Senior Composition
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