2012

Study of Lake Sidrack

A comprehensive study on various chemical species found in Lake Sidrack and their implications.

The University of the West Indies Department of Chemistry, CHEM 2601 Name : Inkiru Bernard ID # : 620022618 Data Submitted : November 26, 2012

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Executive Summary This report contains presents a study done by the CHEM 2601 Environmental Chemistry 2012 laboratory group done over the course of four weeks. The study focused on obtaining water samples from Lake Sidrack found on the campus of the University of the West Indies and assessing them using various parameters. Firstly, a brief introduction describing the reasons the UWI has decided to operate a wastewater treatment facility. This will illuminate both the global and local crisis regarding the lack of inexhaustible potable water sources and to this end has resulted in the reuse of treated wastewater for various purposes. It will give an outline of the treatment facility and the operations that take place. This is concluded by various tables describing both local and international standards for treated wastewater. This is followed by a layout of the various parameters that will be assessed and a brief explanation on these parameters and how quantification will be useful. These parameters are pH, Alkalinity/Acid Neutralizing Capacity, Phosphorus Content, Cation Concentration, Hardness and Conductivity. Once this has been laid out and explained, it will then be shown in the methodology how these parameters are assessed by laying out the method by which the tests were carried out. An attempt is then made to explain the need for quality control and how this necessity is carried out. It then logically follows that the raw data obtained will then be presented in logical, sequential table with data values corresponding to actual measurements made and calculated during the course of the study. After the presentation of the raw data and statistical tests being conducted on suspected outliers and averages found, a serious attempt to analyze the data obtained into tangible conclusions which have a solid grounding in the principles of aquatic chemistry. From the analysis of pH and Alkalinity/ANC data it was found the average pH of the water sample was 7.46 and the average ANC value being 1.39 meq/dm3. From these values it was able to interpret the carbon speciation of the lake and quantify each other various species. This is then followed by presentation and analysis of data and graphs which sought to explain the concentrations of various cations found in the water samples and how this relates to both the hardness and conductivity of the lake. From these analyses, several correlations will be drawn and explained. These correlations attempt to link several parameters and explain these links. For instance, a relationship between hardness and conductivity of water will be introduced an explanation presented to explain this relationship. This will be done for several more parameters. An interpretation of the analysis will be made which then links the results to the purpose of the study which was analyzing treated wastewater using several parameters and the reasons this stated goal was not completely accomplished. The limitations which hampered the study will be discussed and from that a logical conclusion will be drawn which includes recommendations for future studies of this nature.

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Table of Content

Topic Executive Summary Introduction Methodology Presentation of Data Analysis of Data Interpretation of Results Conclusion and Recommendations References Table of Tables

Page (s) 2 4-9 10-11 12-16 17-27 28-31 32 33

Table 1 : Nepa Standards for Wastewater for Horticultural Uses ................................................................. 5 Table 2: NEPA Standards for Irrigation Water ............................................................................................ 5 Table 3 :Environmental Protection Agency Standards for Treated Wastewater4 ........................................ 6 Table 4: Raw Data for Sample 1 ................................................................................................................. 12 Table 5 :Raw Data for Sample 2 ................................................................................................................. 12 Table 6 :Raw Data for [Ca2+], [Mg2+], [CaCO3] and Hardness ................................................................... 13 Table 7: Raw Data for [Na+], [K+] and Conductivity.................................................................................. 13 Table 8: pH and ANC data after outliers have been removed for Sample 1 ............................................... 14 Table 9: pH and ANC data after outliers have been removed for Sample 2 ............................................... 14 Table 10: [Ca2+], [Mg 2+], [CaCO3] and Hardness Data after outliers have been removed. ....................... 19 Table 11: Classification of Water by Calcium Carbonate Concentration ................................................... 22 Table 12: [Na+], [K+] and Conductivity Data after outliers have been removed ........................................ 23 Table 13: Conductivity and TDS measurements for data compiled during study ..................................... 26 Table 14: TDS and Conductivity as it relates to Hardness of Water .......................................................... 28

Table of Figures Figure 1 : Sketch of Lake Sidrack ................................................................................................................. 7 Figure 2: Speciation Diagram of Carbon ................................................................................................... 18 Figure 3: Calcium Carbonate/ Carbon Dioxide Equilibrium ...................................................................... 23

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Introduction The University of the West Indies has undertaken a project which essentially treats wastewater from the university complex and uses the treated water to irrigate the universitys lawn. Ideally, this water would also be used to fill Lake Sidrack. Globally, there is a water shortage epidemic with the lack of potable water being at the forefront of the problem. For this reason, it is essential that the sources of water that are found are made potable to satisfy human consumption and use. To this end, the treatment of wastewater will allow the water sources to be used for human consumption and the treated water used for agricultural and horticultural purposes. Locally, there are several issues that pose threat clean, safe water. These include : There is a challenge with the proper disposal of sewage particularly in communities that are not properly planned. This can lead to several health hazards and various diseases which can have enormous economic, health repercussions. The lack of reliable perennial sources for water and this leads to water rationing which is an untenable situation for a town or a population. Limestone Aquifers provide one of the most pure sources of water. It requires very little treatment. If however, this source is over-tapped then this can lead to the depletion of the water source and the subsequent contamination of the source due to the introduction of anthropogenic activity.

To this end, the University has made the decision to treat the wastewater that emanates from the complex and use it to water the lawns of the campus and put in Lake Sidrack instead of using potable water to do this. Potable water is defined as water which is fit for consumption by humans and other animals. It is also called drinking water, in a reference to its intended use. Water may be naturally potable, as is the case with pristine springs, or it may need to be treated in order to be safe. In either instance, the safety of water is assessed with tests which look for potentially harmful contaminants. Meanwhile, water for agricultural uses does not have to correspond to these stringent standards that are set for potable water
Appendix 1 will shows a schematic representation of the Hermitage Sewage Treatment Plant It will show the location, operation design of the facility and the objective of each stage of the facility. The following table shows the standards for treated wastewater both locally and internationally.

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Table 1 : Nepa Standards for Wastewater for Horticultural Uses

PARAMETER BOD5 TSS Total Nitrogen Phosphates COD pH Faecal Coliform Residual Chlorine EFFLUENT LIMIT 20 ppm 20 ppm 10 ppm 4 ppm 100 ppm 6-9 200 MPN/100 ml 1.5 ppm

The following table shows the NEPA standard regarding water for irrigation purposes.

Table 2: NEPA Standards for Irrigation Water

PARAMETER COD BOD TSS Total Nitrogen Phosphates P pH Faecal Coliform Residual Chlorine Oil and Grease Giardia Cyst EFFLUENT LIMIT <100 ppm 15 15 NA NA NA 12 0.5 10 <1

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The following table shows the standards devised by the United States Environmental Protection Agency in 2004 regarding treated wastewater for various purposes.

Table 3 :Environmental Protection Agency Standards for Treated Wastewater4

The study was designed in a manner in which Lake Sidrack was divided into three sampling sites, from which composite samples were taken. These sites were distinct in that fact that for each parameter that was being tested, a different part of the lake was identified.

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Figure 1 : Sketch of Lake Sidrack

The parameters were : a. pH and ANC b. Cations, Hardness and Conductivity. c. TP and OP This report will focus on pH/ANC, Cations, Hardness and Conductivity Data accrued from the sample and how it relates to the cation-anion balance and interrelationships between them. It will focus on the carbon speciation in the sample. It will also focus on the conductance of the samples and how that relates to the dissolved cations in the sample. The conductance of the sample also relates to the ANC of the water. We will also correlate Hardness and Cations along with SAR etc. This report will show the methodologies used for testing these parameters, their limitations and the accrued results. It will present the results collected and the subsequent interpretations. After the
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presentation, there will be a substantive discussion on the results and what they mean about Lake Sidrak. The parameters chosen have several implications for the overall quality of water and its potential uses. The following paragraphs offer a brief discussion on these parameters and their significance. pH The pH value of water, on a scale of 0 to 14, measures the concentration of hydrogen ions. The pH represents the balance between hydrogen ions and hydroxide ions in water. Solutions with more hydrogen than hydroxide ions have a pH value lower than 7 and are said to be acidic. Solutions with pH values higher than 7 have more hydroxide than hydrogen ions and are said tobe basic, or alkaline. Water with a pH of less than 4.8 or greater than 9.2 can be harmful to aquatic life. Most freshwater fish prefer water with a pH range between 6.5 and 8.4. The pH is also a useful indicator of the chemical balance in water. A high or low pH will adversely affect the availability of certain chemicals or nutrients in the water for use byplants. ANC/Alkalinity Alkalinity is a measure of all the substances in water that can resist a change in pH when acid is added to the water. In other words, alkalinity describes how well water recovers from an acidic punch. Alkalinity is typically expressed in mg/L of calcium carbonate (CaCO 3) because calcium carbonate is a good acid neutralizer. Water with low alkalinity has a low capacity to neutralize or buffer incoming acids and is, therefore, very susceptible to acidic pollution. In contrast, water with greater alkalinity, or buffering capacity, will have the ability to neutralize more of the incoming acidity and therefore resist rapid changes in pH. Sufficient alkalinity in water protects aquatic life against rapid changes in pH and makes water less vulnerable to acid rain. Hardness Waters that contain a significant concentration of dissolved minerals like calcium, magnesium, strontium, iron and manganese, are called hard because it takes a large amount of soap to produce a lather or foam with these waters. When hard waters are heated in water heaters, hot water pipes and boilers, for example, they leave a mineral deposit called scale. Total hardness is expressed as mg/L of calcium carbonate because calcium and carbonate are the dominant ions in most hard waters. The following table gives the concentration of calcium carbonate dissolved in water by its degree of hardness Conductivity/Total Dissolved Solids The electrical conductivity of water is directly related to the concentration of dissolved solids in the water. Dissolved ions in water influence the ability of that water to conduct an electrical current, which can be measured using a handheld conductivity meter. When correlated with laboratory total

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dissolved solids measurements, electrical conductivity can provide an accurate estimate of the total dissolved solids concentration

Phosphorus Concentration Phosphorus, like nitrogen (found in ammonia, nitrite, nitrate), is an important nutrient for plants and algae. Because phosphorus is in short supply in most fresh waters, even a modest increase in phosphorus can cause excessive growth of plants and algae that deplete dissolved oxygen during their growth and as they decompose. Algal blooms colour the water a pea soup green and are a classic symptom of cultural eutrophication. Excessive growth can also reduce the transparency of the water. Much of the excess phosphorus available to plants in the environment comes from farm and lawn fertilizers, runoff containing soil-bound phosphate, yard waste, and runoff from animal feedlots, storm water and certain industrial wastewaters. Total phosphorous includes organic phosphorous and inorganic phosphate. Organic phosphorous is a part of living plants and animals. It is attached to particulate organic matter composed of once-living plants and animals. Inorganic phosphates comprise the ions bonded to soil particles and phosphates present in laundry detergents. All these parameters will be assessed using specific methodologies as described in the following section.

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Methodology5 The methodology employed during this study has two main components, these are : 1. Sample Collection 2. Sample Analysis. Sample Collection. All samples analyzed during this study were collected at Lake Sidrack over a 4 week period from specific areas of the lake. The initial and final weather conditions were noted during the collection period was documented. This was so comparative analysis could be done week to week and how this relates to the data obtained and attempts to explain the variance found in said data. For each week, it was noted whether the fountain/waterfall was active and how this subsequently affected the concentrations of species in the lake. The lake was divided into three specific sample sites from which the composite samples were taken. These three sites were identified as pH/ANC, Phosphorus & Cations and were kept consistent week to week. The samples were collected in a 1M HCl pre-cleaned 1000ml plastic bottles. Sample Analysis Filtration of Sample Each week, once the gross sample was taken, it was taken back to the laboratory for pre-treatment. This was done using a Whatman filter paper from which 250 ml of the filtrate was collected for further treatment before it is analysed for the analyte of choice The three analyses were for : (i) pH/ANC (ii) Total Phosphorus/Ortho Phosphate (iii) Conductance, Hardness and Cations
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The detailed procedures for each analysis can be found in the CHEM 2601Laboratory Manual 2012

Quality Control Quality Control is an essential component when undertaking a study of this nature. It answers the question of reliability ensures that the data obtained is in fact precise and can be relied upon to make informed inferences from. Since we are analyzing fresh water from a lake, it would be prescient to have standards for the various parameters from areas which mimic the conditions found in the lake. Normally, the water found in the lake would be treated wastewater and the standards used would reflect that fact. What could be done, however is to have Quality Control samples taken which are to be assessed. This process is called Internal Quality Control. This can be done by using reference materials to monitor trueness (accuracy) and duplicates in each analysis to monitor precision and to show that the analytical process is under statistical control. In this case, we could use the data collected over previous years as a source of IHRM or have persons not affiliated with course conduct the same tests, using the samples and operating conditions and use those results as some sort of IHRM or guide. Another means of ensuring quality is essential documentation. This includes: a. Document all procedures and activities b. Conduct Quality Control Analyses (as stated above) and Activities c. The data must be stored appropriately where it can be easily accessed for future references d. Monitor Quality Control Results. On the final point, this could be done via the use of Quality Control Charts. These could be used over the duration of the study or over the periods when this annual study is conducted. This will then be able to tell if the system is at any point out of control and from that the reliability of the data can be assessed.

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Presentation of Data These values show the raw data acquired over the four week study. These tables show the pH and Acid Neutralizing Capacity values determined from water samples obtained over a four week period from Sept 12, 2012 to Oct 3, 2012
Table 4: Raw Data for Sample 1 Week 1 pH ANC/meq dm-3 7.14 1.267 7.46 1.694 7.48 1.953 7.01 1.826 6.70 0.495 Week 2 7.49 1.553 7.60 1.398 7.00 1.5357

Week 3 pH ANC/meq dm-3 7.90* 0.3386 6.11 1.293 6.52 0.457 5.49 0.299 7.46 1.257 8.18 1.122

Week 4 7.20 1.257 8.30 1.316 6.65 0.603

Table 5 :Raw Data for Sample 2

Week 1 pH ANC/meq dem-3 7.31 0.630 7.41 1.756 7.48 1.844 7.01 1.899 6.89 0.721

Week 2 7.48 1.383 7.54 0.963 6.82 1.2902

Week 3 pH ANC/meq dem-3 7.68 0.2087 6.15 1.423 6.66 0.438 5.26 0.050 1.063 7.31 0.970

Week 4 7.95 1.313 6.94 1.153 8.44 0.820

*The data in italics represent suspected outliers which we subjected to Q-Tests for clarification.
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These tables show the hardness of the samples, which shows the concentrations of Ca and Mg found in the samples. It also gives values for the calculated hardness in units of meq/dm -3 and [CaCO3]/ppm found in the sample.
Table 6 :Raw Data for [Ca2+], [Mg2+], [CaCO3] and Hardness

Week 1 [Ca]/ppm [Mg]/ppm Hard/meqdm-3 [CaCO3]/ppm No Data 8.10 1.59 No Data 9.34 0.01 No Data
3.80 1.47 73.61959

Week 2

No Data 8.18 4.92

55.07 9.33 1.96

9.45 1.97 2.46

17.51 1.57 2.01 100.2706

17.10 9.37 2.29 114.40804

79.557158 0.5067669

246.0869 97.817064 122.86979

Week 4

Week 4 18.63 2.15 0.57 28.27154 21.65 2.69 0.35 17.5 37.47 3.15 0.57 37.45 3.31 0.41 33.75 3.05 0.35 17.350211

[Ca]/ppm [Mg]/ppm Hard/meqdm-3 [CaCO3]/ppm

18.44 24.47 0.36

36.87 24.49 0.38

27.74 2.75 0.36 17.8414

18.02983 19.19655

28.704912 20.482759

The following tables shows the concentrations of mono-valent cations K+ and Na+ along with the measured conductance found in the samples. These are grouped together due to fact that it is the dissolution of these ions in water that influence the conductance of the sample.

Table 7: Raw Data for [Na+], [K+] and Conductivity.

Week 1 [Na+]/ppm [K]/ppm Conductance/S 13.65 5.37 570.0 14.47 2.50 660 0.49 12.64 2.46 595 9.86 1.79 491 Week 2 13.41 2.33 493 10.24 2.77 524 10.62 2.41 497

No Data 499

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Week 3 [Na+]/ppm [K+]/ppm Conductance/S 0.36 3.00 91.7 0.38 3.35 93.2 0.36 3.78 99.1 0.57 4.33 181 0.35 3.74 259.0 0.57 3.59 112.2

Week 4 0.41 4.02 287 0.35 3.02 255

In the previous tables, several data points have been highlighted as potential outliers. If these values are included in statistical averages, they could incorrectly influence the subsequent conclusions. In light of that, a series of Q tests can be conducted on suspected outliers and from the results of those tests, the data tables can be improved and can then be used to make accurate inferences. From the results of these tests, it is now possible to compose tables containing data from which precise inferences can be made.
Table 8: pH and ANC data after outliers have been removed for Sample 1 pH ANC/meq dm-3 7.14 1.267 7.46 1.694 7.48 1.953 7.01 1.826 6.70 0.495 7.49 1.553 7.60 1.398 7.00 1.5357 7.46 1.257 8.18 1.122 7.20 8.30

1.257 1.315

Average pH = 7.42

Average ANC/meq dm-3 = 1.39

Table 9: pH and ANC data after outliers have been removed for Sample 2

pH ANC/meq dm-3

7.41 1.756

7.48 1.844

7.01 1.899

7.48 1.383

7.54 0.963

7.68 0.2087

6.15 1.423

6.66 0.438

7.31

7.95

6.94

8.44

0.970 1.313 1.153 0.820

Average pH = 7.45

Average ANC meq dm-3 = 1.16

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Graph 1: Variation in pH and ANC for Sample 1 over the course of the study.
9 8 7 6 pH 5 4 3 2 1 0 1 2 3 4 5 6 7 8 9 10 11 12 pH ANC

Graph 2 : Variation in pH and ANC from Sample 2 over the course of the study.

9 8 7 6 5 4 3 2 1 0 1 2 3 4 5 6 7 8 9 10 11 pH ANC/meq dem-3

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Graph 3 : Variation in pH over the period 2009-2012

12 10 8 pH 6 4 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13

2012 2011 2010 2009

Graph 4: Variation of ANC values over a four year period, 2009-2012

8.00 7.00 6.00 ANC/meq/dm3 5.00 4.00 3.00 2.00 1.00 0.00 1 2 3 4 5 6 7 8 9 10 11 12 13 14 ANC 2009 ANC 2010 ANC 2011 ANC 2012

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Analysis of Data pH and Acid Neutralizing Capacity/Alkalinity Over the four weeks in which the samples were taken, the values measured for the pH of water varied from 5.26 to 8.18 with most of the values falling in the 7.0-7.5 range. This is indicative of a very neutral sample which depends on the given week can vary between being slightly acidic to slightly alkaline but maintaining an equilibrium around the value of 7. The pH of water is a measure of the concentration of hydrogen ions in the sample and gives a somewhat limited view of the ability of water to neutralize OH- and other alkaline species. Upon observation of the graph showing the trends in pH over the four year period, it is observed that the pH of the sample are has dropped from an average of 10 to 7. There are several factors that could have caused this noted fall, but it is most likely due to an increase in the acidity in the lake. This could be caused by increased SO 2 levels in the atmosphere which can lead to some acid rain which extended over a period of a few years and has gradually made its way into the water supply. An inference that can be made from the pH values, it is the ideal pH 6.0 8.7 in which fish thrive, which was quite evident as many fish were observed in the sample area over the elapsed time. The most important molecule in the chemistry of water is Carbon Dioxide. It influences not only the pH but also highly affects and dictates that Acid Neutralizing Capacity and Alkalinity of the water sample. Carbon Dioxide is easily dissolved in water and so rainfall is normally slightly acidic, it then produces several ionic species that dictate the extent to which acid will be neutralized, the alkalinity of the solution and the buffer system of water. The species are the bicarbonate ion and the carbonate ion. The process by which CO2 dissolves in water to give the various species as well as their acid dissociation constants are given below. This is the creation of carbon buffer system so to speak. CO2 (g) + H2O (l) HCO3- + H2CO3 (aq) H2CO3(aq) + H2O (l) H3O+(aq) + HCO3-(aq) HCO3-(aq) + H2O(l) H3O+(aq) + CO32-(aq) This buffer system seeks to correct any changes in pH introduced into the system. Which manifestation is present in the species is a product of pH. The carbon speciation diagram below shows how this is determined.

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Figure 2: Speciation Diagram of Carbon

From the average pH values calculated 7.44 and 7.42 it is clear that the HCO3- is the major carbon species in the water and plays the most important role in neutralizing acid and towards the overall alkalinity of the sample. It is found the average ANC/Alkalinity values were 1.39 and 1.19 meq dm-3 for Samples 1 and 2 respectively. These values mean that these were the amount of acid that the water is able to fully neutralize those respected volumes of acid. From these values, the Carbon Speciation of the water sample can be calculated. Using Sample 1 : The alkalinity in ppm CaCO3 = (1.39 meq/dm3 * 50) = 69.5 ppm CaCO3 pH = 7.44 , therefore pOH = 6.56 [OH-] = 2.75 x 10-7 M or 2.75 x 10-4 mM 1.39 meq/dm3 = 2.75 x 10-4 + [HCO3-] + 2[CO32-] 10-7.44 [CO32-] = Ka2[HCO3-]/[H+] Since {Ka2 = [H3O+][CO32-]/ [HCO32-]} Hence, [CO32-] = 4.63 x 10-11 [HCO3-]/3.6 x 10-8 1.39 meq/dm3 = [HCO3-] + 2{ 4.69 x10-11 [HCO3-]/3.6 x10-8} =[HCO3-]{ 1 + 2(4.69 x 10-11)/ 3.6 x 10-8}
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=[HCO3-]{1 + 2(1.302 x 10-4)} [HCO3-] = 0.99 mM Since 2[CO32-] = (1.39 - 0.99)mM [CO32-] = 0.2 mM =

Alkalinity = 69.5 ppm CaCO3 [OH-] = 2.75 x 10-4 mM [HCO3-] = 0.99 mM [CO32-] = 0.2 mM

The following tables present data describing the hardness of the water samples and the associated cations which significantly contributes to the hardness of the water sample. The data is one which has been analyzed for outliers and has been removed which could have led to erroneous conclusions.

Table 10: [Ca2+], [Mg 2+], [CaCO3] and Hardness Data after outliers have been removed.

[Ca2+]/pp m [Mg2+]/pp m Hard/meqd m-3 [CaCO3]/p pm

55.07

9.45

17.51

18.44

36.87

27.74

18.63

9.33

1.97

1.57

24.47

24.49

2.75

2.15

1.96

2.46

2.01

0.36

0.38

0.36

0.57

97.817064

122.86979

100.2706

18.02983

19.19655

17.8414

28.27154

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Table 10 ctd.

[Ca2+]/ppm [Mg 2+]/ppm Hard/meqdm-3 [CaCO3]/ppm

21.65 2.69 0.35 17.5

37.47 3.15 0.57 28.7049

37.45 3.31 0.41 20.482759

33.75 3.05 0.35 17.350211

The following graphs show the variation of the [Ca2+], [Mg2+], Hardness in meq/dm3 and ppm CaCO3. Graph 5 : Variation in [Ca2+] over the course of the study

[Ca2+]/ppm
40 30 20 10 0 1 2 3 4 5 6 7 8 9 [Ca]/ppm

Graph 6 : Variation in [Mg2+] over the course of the study.

[Mg2+]/ppm
4 3 2 1 0 1 2 3 4 5 6 7 8 [Mg]/ppm

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Graph 7: Variation in Hardness over the course of the study

Hard/meqdm-3
3 2.5 2 1.5 1 0.5 0 1 2 3 4 5 6 7 8 9 10 11

Hard/meqdm-3

Graph 8 : Variation in [CaCO3] over the course of the study.

[CaCO3]/ppm
140 120 100 80 60 40 20 0 1 2 3 4 5 6 7 8 9 10 11

[CaCO3]/ppm

Hardness of Water The hardness of water is a measure of the CaCO3 present in a sample of said water. Hardness is mostly associated with the ability of water to properly precipitate soap. However, in terms of chemistry hardness is thought of as the sum of the multivalent cation concentrations dissolved in water. Normally, the most common multivalent cations found in fresh water are Calcium and Magnesium. Hardness is normally quantified by the carbonates of these cations but in the case primarily the CaCO3. It is normally recorded in equivalents of said carbonate and is classified according into categories of soft, moderately hard, hard and very hard. These are shown below:

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Table 11: Classification of Water by Calcium Carbonate Concentration Classification Soft Moderately Hard Hard Very Hard CaCO3 equivalent (ppm) <75 75-150 150-300 >300

From the calculated values in the tables above, it is now easy to categorize the water found in Lake Sidrack as soft to moderately hard. From the data above, it was seen that concentration of calcium carbonate in the lake averaged around ~ 106.33 ppm which could be classified as moderately hard water, but the final two week of the study saw a dramatic drop in the concentration of CaCO3 to it averaging about ~23.57ppm which moves its classification to soft water. This could be due to decreased CO2 dissolution in the water and/or increased weathering of the rocks. The CaCO3 found in natural water has several sources and there are various factors the concentration day to day or over several years. Temporary hardness is due to the presence of calcium and bicarbonate ions in water and may be eliminated by boiling the water. Ca2+ + 2HCO3- CaCO3 (s) + CO2 (g) + H2O The reverse reaction causes CO2 to be lost from the water and CaCO3 deposits are formed as shown in the diagram below.

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Figure 3: Calcium Carbonate/ Carbon Dioxide Equilibrium

The CO2 dissolved in water that is gained by equilibration with the atmosphere is not sufficient to account for the dissolved calcium in water. Rather the respiration of micro-organisms degrading organic matter in water, sediments and soil { (CH2) + O2 CO2 + H2O )}, and accounts for the high levels of CO2 and HCO3- in water. From the data accrued it can be observed that the hardness of the water sample was relatively high in the first week but fell drastically in the final two weeks. This could be due to a decrease in the amount of carbon dioxide in the water which results from less aquatic life being found in the lake. This was observed in those two weeks as the water level of the lake has risen and the amount of fish in the lake seemed to have decreased. Or the lake has become more dilute meaning that the concentration of both Ca and Mg in them have decreased causing the overall hardness of the water to fall. Alkalinity and Hardness of Water Alkalinity and Hardness are related through the common ions formed in aquatic systems. Specifically, the counter-ions associated with the bicarbonate (HCO3-) and carbonate (CO32-) fraction of alkalinity is the principal ions responsible for hardness (usually Ca2+ and Mg2+). As a result, the carbonate fraction of hardness (expressed as CaCO3 equivalents) is chemically equivalent to the bicarbonates of alkalinity present in water in areas where the water interacts with limestone. Therefore, any hardness of water greater than the alkalinity represents non-carbonate hardness. The following tables show the concentration of the ionic salts Na and K in the water sample as long as its measured conductivity.

Table 12: [Na+], [K+] and Conductivity Data after outliers have been removed
[Na+]/ppm [K+]/ppm 12.64 2.46 9.86 1.79 13.41 2.33 10.24 2.77 0.36 3.00 0.38 3.35 0.36 3.78 0.57 4.33 0.35 3.74 0.57 3.59 0.41 4.02 0.35 3.02

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Conductivity/S

595

491

493

524

91.7

93.2

99.1

181

259.0

112.2

287

255

The following graphs show the trend of [Na+], [K+] and Conductivity over the study period. Graph 9: Variation of [Na+] over the course of the study

[Na+]/ppm
15 10 5 0 1 2 3 4 5 6 7 8 9 10 11 12 [Na+]/ppm

Graph 10: Variation of [K+] over the course of the study

[K+]/ppm
5 4 3 2 1 0 1 2 3 4 5 6 7 8 9 10 11 12 [K]/ppm

Conductivity/S
700 600 500 400 300 200 100 0 1 2 3 4 5 6 7 8 9 10 11 12

Graph 11 : Variation in Conductivity over the course of the study

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Graph 12 : Trends in Conductivity over the period 2009-2012

1000 900 800 700 600 500 400 300 200 100 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Conductivity 2009 Conductvity 2010 Conductivity 2011 Conductivity 2012

Conductivity is a measure of the ability of water to pass an electrical current. Conductivity in water is affected by the presence of inorganic dissolved solids such as chloride, nitrate, sulfate, and phosphate anions (ions that carry a negative charge) or sodium, magnesium, calcium, iron, and aluminum cations (ions that carry a positive charge). Organic compounds like oil, phenol, alcohol, and sugar do not conduct electrical current very well and therefore have a low conductivity when in water. Conductivity is also affected by temperature: the warmer the water,
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the higher the conductivity. For this reason, conductivity is reported as conductivity at 25 degrees Celsius (25 C). Based on the graphs above, it can seen that when the [Na+] was high, the conductivity of the lake was found to be high as well, reaching ~500S, this also corresponds to comparatively low [K+]. However, in the final two weeks, the exact reverse occurred it was seen that the [Na+] decreased while the [K+] increased and the conductivity decreased. It can be then reasonably assumed that the conductivity of water is directly related to the concentration of sodium in it with the potassium concentration playing mainly a background role. These ionic salts have the tendency to be completely dissolved in water, and due to their size tend to conduct electricity. However a more accurate method of analyzing the conductivity of a solution would be to analyze the total dissolved solids in the water sample. This will give a broader view of the conductivity of the solution as it encompasses not only the ionic salts but any other compound that may cause a change in the overall conductivity of the solution.

To find the TDS/ppm from the conductivity data : TDS/ppm = 0.64 S/cm at 25C Using that conversion factor, the TDS/ppm of the sample was determined and tabulated.

Table 13: Conductivity and TDS measurements for data compiled during study
Conductivity /S TDS/ppm 595 491 493 524 91.7 93.2 99.1 181 259 165.7 6 112.2 287 255

380.8

314.24 315.52

335.36

58.688

59.648

63.424

115.84

71.808

183.68

163.2

When the salt concentration reaches a certain level, electrical conductivity is no longer directly related to salts concentration. This is because ion pairs are formed. Ion pairs weaken each other's charge, so that above this level, higher TDS will not result in equally higher electrical conductivity. Using this classification as a guide, the water can be easily classified by its TDS/ppm value. Fresh: <1,000 ppm TDS Brackish: 1,000-5,000 ppm TDS Highly Brackish: 5,000-15,000 ppm TDS
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Saline: 15,000-30,000 ppm TDS Sea Water: 30,000-40,000 ppm TDS Brine: 40,000-300,000+ ppm TDS

It is quite clear from the values obtained that the value lies well in the range of fresh water.

Temperature From the data gathered, the temperature of the sample area was found to be in the range of 28 - 31C which upon analysis does not have much variance and is unlikely to greatly influence the various parameters that have been measured. However, temperature can affect the amount of concentration of dissolved oxygen in the water which affects the available oxygen for organisms in the sample area. This in turn affects the carbon dioxide concentration in water. This then affects the alkalinity, hardness as well as the pH of the water which are all influenced by the carbon speciation.

Hardness and Conductivity3

Water hardness is the measurement of the amount of ions which have lost two electrons (divalent cations) dissolved in the tested water and is therefore, related to total dissolved solids. The more divalent cations dissolved in the water the "harder" the water. Generally the most common divalent cations are calcium and magnesium, however other divalent cations may contribute including iron, strontium, aluminum, and manganese.

TDS(ppm)
0-70 70-150 150-250

Conductivity(uS/cm)
0-140 140-300 300-500

Hardness Very Soft Soft Slightly Hard

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Total dissolved 320-420 640-840 Hard solids (TDS) Above 420 Above 840 Very Hard refers to a measure of all inorganic solids dissolved in the water. This means that it will measure ions that contribute to water hardness, tike calcium, but also those that do not, like sodium. The TDS measurement is a better reflection of the total mineral content of the water rather than a water hardness measurement. TDS measurements can also be derived from relative conductivity measurement.
250-320 500-640 Moderately Hard

Table 14: TDS and Conductivity as it relates to Hardness of Water

Interpretation of the Results 28 | P a g e

The study was designed to allow three broad parameters to be assessed over four weeks. This allowed the each group of persons to repeat their analysis of a parameter. It was also designed so that each week, all groups would not be conducting the same analysis. This allowed for documentation of the data over the four week from which contrasts and similarities can be drawn. In my view, this is an efficient and prudent way of organizing the study as it gives all groups exposure to the process of proper sample collection and treatment. It also gives room for improvement of the carrying out of the analysis, due to the fact that after each week each group is now armed with knowledge of how the methods work and this can be shared with groups that will conduct those tests the following week. It also allows the group a chance to re-do their first analysis. These results are now more reliable because the group would have prior experience with the procedure and therefore can now properly organize their work to efficiently carry out said plan. In that respect, it improves the quality of the data. This is due to the fact that for each week, there was careful planning of the activities to be undertaken during the analysis. For each week, the previous analysis done was used as guide for the implementation of this weeks analysis. This makes the data more credible due to the design previously described. However, is to be noted that these interpretations are made within the context of several factors that could limit the use of the data. It was originally intended that the analysis be carried out on treated wastewater which is normally supposed to be used as the source of the water in the lake. However, this year that is not the case as the water in the lake is one that is treated by the National Water Commission and is unlikely to contain the nutrients in the same concentration as the wastewater. That in itself imposes a limitation on the broad interpretation of the results in respect to using as reference for the usability of wastewater in man-made ponds. In turn, this makes it difficult the success or failure of wastewater treatment due to the source of the sample. This could however, be used as a goal for future treated wastewater. It was seen over the course of the study that there was thriving marine life within the lake, which indicates that the conditions provided by the water were adequate to sustain life. It therefore can be argued that properly treated wastewater should have the same effects on aquatic life.

It is with the context of this that we assess the appropriateness of treated wastewater for agricultural purposes or other reuse. 29 | P a g e

The following diagram for the United Nations (as devised by Edwards 2000) gives a schematic representation of the possibilities for the reuse of treated wastewater. Diagram 4 : Schematic for the use of treated wastewater

The United Nations gives the following guidelines for the use of treated wastewater for irrigation purposes1:

Treated wastewater from off-site treatment plants can be reused for irrigation of parks and gardens, agriculture and horticulture, tree plantation and aquaculture, if these exist or can be established not far from the wastewater treatment plants. For these purposes the wastewater should generally be treated to secondary wastewater standard (< 20 mg/L BOD and < 30 mg/L SS). Total coliforms should be < 1000 organisms per 100 mL for irrigation by spraying. When sub-surface irrigation is used this requirement may not be necessary. A period of nonentry to irrigated sites may need to be observed, particularly for wastewater-irrigated parks and gardens. Irrigation of vegetables for direct human consumption requires a much stricter guideline. Because requirement of wastewater for plant growth is governed by climatic conditions, soil and plant type, there may be a need for storage of the wastewater. An alternative to storage, if land area is not available for this purpose, is to dispose of wastewater that is excess to requirement

To this respect the Organization of American States lists several advantages and disadvantages to the reuse of wastewater2.

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Advantages

This technology reduces the demands on potable sources of freshwater.

It may reduce the need for large wastewater treatment systems, if significant portions of the waste stream are reused or recycled. The technology may diminish the volume of wastewater discharged, resulting in a beneficial impact on the aquatic environment. Capital costs are low to medium, for most systems, and are recoverable in a very short time; this excludes systems designed for direct reuse of sewage water. Operation and maintenance are relatively simple except in direct reuse systems, where more extensive technology and quality control are required. Provision of nutrient-rich wastewaters can increase agricultural production in water-poor areas. Pollution of seawater, rivers, and groundwater may be reduced. Lawn maintenance and golf course irrigation is facilitated in resort areas. In most cases, the quality of the wastewater, as an irrigation water supply, is superior to that of well water. Disadvantages If implemented on a large scale, revenues to water supply and wastewater utilities may fall as the demand for potable water for non-potable uses and the discharge of wastewaters is reduced. Reuse of wastewater may be seasonal in nature, resulting in the overloading of treatment and disposal facilities during the rainy season; if the wet season is of long duration and/or high intensity, the seasonal discharge of raw wastewaters may occur. Health problems, such as water-borne diseases and skin irritations, may occur in people coming into direct contact with reused wastewater. Gases, such as sulphuric acid, produced during the treatment process can result in chronic health problems. In some cases, reuse of wastewater is not economically feasible because of the requirement for an additional distribution system. Application of untreated wastewater as irrigation water or as injected recharge water may result in groundwater contamination. Limitations on the Study
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The limitations on the study stem from the sampling. The fact that the sample was taken at a specific time and date, makes it clear that the figures calculated represent a snapshot at that particular time. The gross sampling area, Lake Sidrack is itself a dynamic medium which has a fountain which is operating some of the time. In that regard, when the fountain is in use, the species found in the lake can undergo mixing and is therefore susceptible to different concentrations being obtained week to week. This can be overcome by ensuring that the lake is kept in a somewhat standard mode. This means that the operation of the fountain must be on some consistent schedule which would allow more faith to be put into the samples taken at any particular time that they would be a true representation of the population.

Conclusions and Recommendations 32 | P a g e

When the introduction is taken into consideration along with the benefit of hindsight, there are several conclusions that can be drawn based on the results derived. Since the majority of the report is concerned with the pH, ANC/Alkalinity, cation concentration, hardness and conductivity of water samples gathered from Lake Sidrack, the major conclusions are focused on that data. When focusing on the pH and ANC/Alkalinity of the sample, it was found that the average pH of the sample was ~7.42 with an ANC/Alkalinity of 1.39. Given these values, it was determined by the carbon speciation diagram, that [HCO3-] was the dominant carbon species influencing the alkalinity of the water. The [HCO3-] was found to be 0.99mM and the [CO32-] found to be 0.2mM and the [OH-] calculated at 2.75 x 10-4mM. The alkalinity was also translated to be 69.5 ppm of CaCO3. The data relating the potential hardness of the samples was analyzed and presented. It was seen that the hardness of the water sample could be categorized as hard water but in the final two weeks of the study the water was now soft water. An explanation of the chemical principles which influence the CO2/CaCO3 balance in water was offered and it was found that this was possibly due to decrease amounts of CO2 in the lake. There was also an analogy made between the alkalinity of the water and its hardness and it was found that the hardness reflected any additional inorganic species which will neutralize acids, these species also tend to be non-organic, such as hydroxide ions. Following this, the conductivity of the water sample was analyzed and it can be concluded that the conductivity of water is directly proportional to the sodium concentration found in the water. This then led to the total dissolved solids being calculated. It was concluded that the conductivity of water is not always related to the concentration of the total dissolved solids. With these values being calculated, it was found the they were totally consistent with what is normally found in fresh water. In light of all these conclusions, it can be seen that all the parameters fall within the category of soft, freshwater with a neutral pH which bodes well as it is potable water provided by the National Water Commission. This herein lies the problem, it not possible to draw broad conclusions on the nutrient content of treated wastewater as it is relatively certain that these values are not transferrable. In the future, it is recommended that a genuine effort is made to obtain actual treated wastewater sample as this hampers the actual goal of the study. The study exposed us the rigors and techniques involved in water sampling and the experience gained from that will assuredly be used in future endeavours.

References 1. United Nations Website, Last Accessed November 24, 2012 http://www.unep.or.jp/ietc/publications/freshwater/sb_summary/12.asp

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2. Organization of American States Website, Last Accessed November 24, 2012 http://www.oas.org/dsd/publications/Unit/oea59e/ch26.htm

3. University of Florida Website, Last Accessed November 23, 2012 http://edis.ifas.ufl.edu/ss540

4. United States Environmental Protection Agency Website, Last Accessed November 24, 2012 http://www.epa.gov/nrmrl/wswrd/dw/smallsystems/pubs/625r04108.pdf

5. University of the West Indies, CHEM 2601 Laboratory Manual 2012

Appendices

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