Lecture Notes_LPP Module 1 PDF

ENVENG 200 Fundamentals of Environmental Engineering Introduction Why are we here?  Introduction Humanity’s Top Ten Problems over Next 50 Years: 1. Energy 2. Water 3. Food 4. Environment 5. Poverty 6. Terrorism and War 7. Disease 8....

ENVENG 200 Fundamentals of Environmental Engineering Introduction Why are we here?  Introduction Humanity’s Top Ten Problems over Next 50 Years: 1. Energy 2. Water 3. Food 4. Environment 5. Poverty 6. Terrorism and War 7. Disease 8. Education Source: https://en.m.wikipedia.org/wiki/File:Earth_Eastern_Hemisphere.jpg Last Accessed: July 16, 2018 9. Democracy 2020: 7.8 Billion People 10. Population 2050: 10 Billion People Adapted from Richard Smalley’s talk at MIT in 2003 4  Introduction What is Environmental Engineering - “Environmental engineering is manifest by sound engineering thought and practice in the solution of problem of environmental sanitation, notably in the provision of safe, palatable, and ample public water supplies; the proper disposal of or recycle of wastewater and solid wastes; soil and atmospheric pollution, and the social and environmental impact of these solutions.” – ASCE - “Environmental engineering is the integration of science and engineering principles to improve the natural environment (air, water, and/or land resources), to provide healthy water, air, and land for human habitation (house or home) and for other organisms, and to remediate pollution sites” – Wikipedia 5  Introduction Learning Objectives (LPP Module) - Recognise the interdisciplinary nature of environmental engineering - Understand and interpret environmental standards, regulations, and measurements - Obtain the necessary background for subsequent courses in drinking water, stormwater, and wastewater treatment. 6  Module Structure Week 1 – Introduction to Environmental Engineering Week 2/3 – Environmental Measurements Week 3/4 – Three Waters Week 4/5 - Guest Lectures and Test 1 7  Course Reading Richard O. Mines (2014) Environmental Engineering Principles and Practice, Wiley 8  Course Expectations Your Responsibilities - Academic integrity - Prepare well (class notes and reading materials) - Be regular - Respect for everyone present in the class - No external website browsing - Cell phones in silent mode - Don’t come late and/or leave early - No foods and drinks in the classroom Our Goal Have FUN while learning environmental engineering 9  Academic Integrity Why is academic integrity important? Student Academic Conduct Statute (2020): “Such integrity maintains the reputation and quality of its qualifications and protects their international recognition.” Engineering New Zealand’s Code of Ethical Conduct: “In performing, or in connection with, your engineering activities you must act with honesty, objectivity, and integrity …” Academic dishonesty has long-term consequences. 10 Academic Integrity at UoA and FoE 120 misconduct cases (coursework and exam, incl. plagiarism, collusion, contract cheating, etc.) in the Faculty of Engineering in 2020. The cases are recorded in the Register of Academic Misconduct. Information about Academic Integrity at the University of Auckland can be found here: https://www.auckland.ac.nz/en/staff/lea rning-and-teaching/academic- integrity.html 11  ENVENG 200 Fundamentals of Environmental Engineering Dr. Lokesh P. Padhye Global Environmental Issues  Learning Objectives Understand climate change Understand greenhouse gases Understand ocean acidification 2 Global Environmental Issues So, what are the top global environmental challenges? How do you determine top 5, 10, or whatever number? 3  Global Environmental Issues Climate Change Green house gas emissions Ocean acidification Environmental Pollution Air, water, soil Emerging contaminants Resource Depletion Renewable and non-renewable Un-sustainability 4 Big Picture Big History Project: David Christian 5  Climate and Climate Change Climate: a region’s long-term pattern of atmospheric conditions Global climate change: changes in Earth’s climate, including temperature, precipitation, and other variables Global warming: an increase in Earth’s average surface temperature Climate changes naturally, but the recent rapid warming of the planet and its change in atmospheric composition are widely thought to be due to human activities. Three factors that influence climate more than anything: sun, atmosphere, and oceans. Humans are influencing two of those. 6  Greenhouse Gases Atmospheric gases that absorb the emanating radiation from earth’s surface are greenhouse gases. By absorbing and re-emitting this radiation, they warm Earth’s atmosphere and surface, like a greenhouse. This is popularly called the greenhouse effect. Global warming potential can be defined as the relative ability of one molecule of a given greenhouse gas to contribute to global warming. 7 Greenhouse Effect 8  Greenhouse Gases Carbon dioxide is a primary greenhouse gas But molecule for molecule: Halocarbon gases (which include CFCs) are powerful greenhouse gases. But their effects are slowing due to the Montreal Protocol. Water vapor is the most abundant greenhouse gas. Its future changes, if any, remain uncertain. 9  Greenhouse Gases CO2 concentration has increased 33% in the past 200 years. It is now at its highest level in 400,000 years, and probably 20 million years. Due mainly to burning of fossil fuels (source) and deforestation (destroying sink) Methane has increased to more than 150% since 1750; due mainly to fossil fuels, landfills, cattle, and rice crops Nitrous oxide has increased by 17% since 1750; due mainly to feedlots, chemical plants, auto emissions, agricultural practices 10  Climate and Climate Change Other Factors: Aerosols (microscopic particles and droplets) in the atmosphere can: warm the climate (soot), or cool the climate (sulfates) Sulfate-rich volcanic eruptions can cool Earth temporarily. Milankovitch cycles 11  Climate and Climate Change Milankovitch Cycles Variation of Earth’s tilt Wobble of Earth’s axis Variation of Earth’s orbit These 3 types of cycles also affect climate in the long term. 12  Oceans and Climate The oceans also affect the planet’s climate. Surface currents carry warm water from equatorial regions to the North Atlantic, then cool and sink. This keeps Europe warmer than it would be otherwise. 13  Oceans and Climate If global warming causes enough of Greenland’s ice sheet to melt, freshwater runoff into the north Atlantic could shut down current and abruptly change the climate of Europe and eastern North America. Such “abrupt climate change” would not be as rapid and dramatic as in the fictional Hollywood movie “The Day After Tomorrow,” but would have major consequences nonetheless. 14 Oceans and Climate The best-known interactions between oceans and climate are El Niño and La Niña events. In normal conditions, winds push warm waters (red) to the western Pacific Ocean. This allows cold water to well up from the deep in the eastern Pacific. In an El Niño event, winds weaken, warm water sloshes to the east, and prevents the cold upwelling. La Niña is the opposite 15  Climate and Climate Change Ice caps and glaciers accumulated over thousands or millions of years. They contain bubbles of gas preserved from the time when each layer formed. Scientists drill cores and analyze the gas bubbles in each layer to see what the atmosphere was like then. 16  Climate and Climate Change Scientists also drill cores into the sediments of ancient lake beds. By identifying types of pollen grains in each layer, they can tell what types of plants were growing there at the time. Sources of this type of indirect evidence are proxy indicators. 17  Climate and Climate Change To predict what will happen to climate in the future, scientists use climate models: Computer simulations that use known behavior of past climate to analyze how climate should behave as variables are changed. Coupled general circulation models (CGCMs) are models that combine, or couple, the effects of both atmosphere and ocean. Today’s highly complex CGCMs incorporate many factors in order to predict future climate changes. 18 Climate and Climate Change Natural or anthropogenic factors ONLY = poor fit. BOTH types of factors = excellent fit. 19  Climate and Climate Change In 2001, the world’s climate scientists combined to produce the single most comprehensive and authoritative research summary on climate change: The Third Assessment Report of the Intergovernmental Panel on Climate Change (IPCC), which summarized all scientific data on climate change, future predictions, and possible impacts. The IPCC report established that global temperature is rising. 20 Climate and Climate Change The IPCC also reported findings on physical changes: Average sea level increased 10–20 centimeters (4–8 inches) during 20th century. 2 weeks less ice cover on northern lakes and rivers. Arctic sea ice thinned 10–40% in recent decades. Mountain glaciers melted back worldwide. Snow cover decreased 10% since satellite observations began. Growing season lengthened 1–4 days each decade over the past 40 years. 21 Climate and Climate Change Biological changes were also found by the IPCC: Geographic ranges of many species have shifted toward the poles and up in elevation. In spring, plants are flowering earlier, birds migrating earlier, animals breeding earlier, and insects emerging earlier. Coral reefs are “bleaching” more frequently. 22  Climate and Climate Change Global warming is causing glaciers to shrink and polar ice shelves to break away and melt. The increased flow of water into the oceans lead to sea level rise. Sea level is also rising because ocean water is warming, causing water to expand in volume. Higher sea levels lead to beach erosion, coastal flooding, intrusion of saltwater into aquifers, etc. 23  Climate and Climate Change The IPCC and other groups have predicted future impacts of climate change in this century: Temperature will rise 3–5°C. Droughts, floods, snowpack decline, and water shortages will create diverse problems. Temperature extremes will cause health problems; tropical diseases will move towards polar directions. Sea level rise will flood coastal wetlands, real estate. Ecosystems will be altered; some will disappear. 24  Oceans and Climate Most of the Past 60 years of Global Warming Has Gone into the Oceans The Ocean has absorbed approximately 93% of the warming of the Earth system that has occurred since 1955. The top 700m ocean layer accounted for approximately 2/3 of the warming of the 0-2000m layer of the World Ocean. Without the ocean to absorb greenhouse gas heating, atmosphere would have warmed by more than 20 °C, or 45 times hotter temperature difference! Oceans are also good storage for carbon dioxide, but is this good? 25  Oceans and Climate Raising ocean acidity means more H+ ions, which combine with carbonate ions to produce bicarbonate, and thus prevent those carbonate ions from instead combining with Ca in metabolism of phytoplankton, algae, and sea animals to produce CaCO3 or seashell 26 Oceans and Climate 27  Oceans and Climate Rising CO2 goes with falling (more acidic ) pH: Partial pressure of CO2 in the ocean vs ocean pH (seasonal oscillations due to phytoplankton blooms, mostly). CO2 pressure has risen by fully 10% in just the past two decades, as pH falls. 28  Oceans and Climate pH in the Caribbean Sea; prime habitat for coral reefs – from 1988-2008. Clearly, becoming more acidic. Large shift in marine species to be expected in the future, as corals and other aragonite-forming species disappear. 29  Key Messages Many factors shape global climate. Scientists and policymakers are beginning to understand anthropogenic climate change and its impacts more fully. Many scientists and policymakers are deeply concerned. As time passes, fewer experts are arguing that the changes will be minor. Sea-level rise will affect developed and developing countries alike. 30  Key Messages 93% of global warming heat since 1955 is now in the oceans Water’s hydrogen bonds give it very high thermal capacitance; sea surface temperatures risen to much lesser extent than air temperatures Without ocean heat uptake, human-induced greenhouse warming of atmosphere would have led to raising surface temperatures by 45 times the current temperature change. CO2 we force into atmosphere slowly dissolves in ocean, raising acidity. Rising acidity (consumption of carbonate ions), inhibits carbonate formation within sea plants and animals. 31  ENVENG 200 Fundamentals of Environmental Engineering Dr. Lokesh P. Padhye Global Environmental Issues  Learning Objectives Understand environmental pollution Understand contaminants in the environment 2  Environmental Pollution Presence in the environment of an agent which is potentially damaging to either the environment or human health. (Briggs, 2003) As such, pollutants come in many forms, including chemicals, organisms and biological materials, as well as energy in its various forms (e.g., noise, radiation, heat). Environmental compartments: – Air – Water – Soil and Sediments 3  Pollutants Over the last 100 years, we have benefited from new drugs, industrial chemicals, and other products in our quest for “better living through chemistry.” A Water Environment Federation paper estimated 80,000 different chemicals were released into the environment over this time. 4  Pollutants Organics PPCPs PFAS Persistent Organic Pollutants Nanoparticles Emerging Contaminants Microplastics Inorganics/Heavy Metals Biological Some of these substances are found naturally in environment Others are natural substances that are concentrated by anthropogenic activities And still others are manmade chemicals that do not occur in nature 5 Emerging Contaminants 6 Pharmaceuticals The human impulse for a cure runs quite deep, and our first instinct whenever we feel sick or heading toward sickness is to medicate. Pharma-Ecology, 2008 Human and veterinary substances taken in response to disease/maladies. Some of these pass through our body unmetabolized Unused drugs are disposed of through toilets or rubbish Some of the antibiotics released can encourage antibiotic resistant genes in the environment 7 Personal Care Products Compounds used in our daily lives Soaps, detergents, perfumes, aftershaves, cleaning agents, disinfectants, sprays, deodorants, bug sprays, sunscreens, personal hygiene products, etc. End up in our waterways through showers, sinks, toilets Source: https://indiebusinessnetwork.com/personal-care-products-safety-act-of-2015/ (Last Accessed – July 2018) 8 Endocrine Disruptors ‘Endocrine Disrupting Compounds/Chemicals’ (EDCs) are substances that mimic a hormone in the endocrine system and disrupt the function of the hormone. Linked to biological effects in animals. May stimulate growth or cause underproduction of hormones. Concern: low-level but prolonged exposure may cause similar effects in humans. 9 Endocrine Disruptors DDT Bisphenol A (BPA) – plastic water bottles, white vegetable can liners Estrogenic substances - birth control pills Pthalates - in toys and air fresheners Fire retardants Source: https://desdaughter.com/2016/12/02/endocrine-disruptors-the-manufacture-of-a-lie/ (Last Accessed – July 2018) 10 Disinfection By-Products (DBPs) DBPs are formed when water/wastewater disinfectants react with organics present in the matrix to form more toxic compounds Suspected Carcinogens Suspected to affect reproduction Large population exposure to DBPs Traditional DBPs include: trihalomethanes, haloacetic acids Emerging DBPs include: Nitrogenous DBPs like nitrosamines 11 Plastic (Microplastics) Microplastics (>70% 23  kWh/m3 0.001 0.01 0.1 1 10 C hl or U in V e (D is in fe ct io n ) O zo n e O zo n e- A O P U Treatment V- A O P R O R O -U V- AO P Energy per Unit Volume for Water 24  Greenhouse Climate Gas Change Emissions Impact Cycle Novel Treatment Drought Technologies Increased WW Population Influence Growth On DW 25  Key Messages Pollutants documented in water for > 50 years If we look hard enough, we will find pollutants No treatment process is “perfect” Pollutant reduction vs. pollution relocation Cleaner water vs. carbon footprint 26  ENVENG 200 Fundamentals of Environmental Engineering Dr. Lokesh P. Padhye Measurements and Standards  Class Objectives Understand environmental standards Understand the water quality parameters Understand their measurement and standards 2  Environmental Standards National environmental standards (NES) are regulations which prescribe technical standards, methods or requirement for land use and subdivision, use of the coastal marine area and beds of lakes and rivers, water take and use, discharges, or noise. They can also prescribe technical standards, methods or requirements for monitoring. NZ Drinking Water Standards (NZDWS): Maximum acceptable value (MAV) for drinking water – the concentration of a determinand below which the presence of the determinand does not result in any significant risk to a consumer over a lifetime of consumption. 3 Source: https://reliefweb.int/map/world/proportion-population-using-improved-drinking-water-sources-2000 Last Accessed: July 16, 2018 4  Water Quality Parameters pH Alkalinity Conductivity Salinity Dissolved oxygen (DO) Turbidity Total dissolved solids (TDS) Hardness Temperature Source: http://www.waterlux.com/blog/lead-arsenic-and-other-contaminants-in-fort- lauderdale-drinking-water/ Last Accessed: July 2018 Pathogens Biochemical oxygen demand (BOD) Chemical oxygen demand (COD) Emerging Contaminants 5  Water Uses Use Typical Monitored Parameters Public Water Supply Turbidity, TDS, inorganic and organic compounds, microbes Water contact recreation Turbidity, bacteria, toxic compounds Fish propagation and wildlife DO, chlorinated organic compounds Industrial water supply Suspended and dissolved constituents Agricultural water supply Sodium, TDS Shellfish harvesting DO, bacteria 6 Freshwater Criteria (U.S. EPA) Criteria Recommended Standard pH 6.5-9.5 Alkalinity 20 mg/L or more Dissolved Oxygen 30 day average 5.5 mg/L (warm water fish) Suspended Solids Should not reduce photosynthesis by more than 10% in the water 7  Drinking Water Criteria (U.S. EPA) Criteria Recommended Standard Reason Coliform Bacteria 0 colonies/ml Health pH 6.5-8.5 Aesthetic Barium 2 mg/L Health Nitrate 10 mg/L Health Total Dissolved 500 mg/L Taste Solids 8  pH Measures hydrogen ion concentration Negative log of hydrogen ion concentration Ranges from 0 to 14 std. units pH – 7 neutral – 0 - 7 acidic – 7 - 14 alkaline Source: http://cerceteaza.blogspot.com/2011/05/ph-ul-potentialul-de-hidrogen.html Last Accessed: July, 2018 Source: https://hannainst.com/hi99121-ph- meter-for-direct-soil-measurement.html Last Accessed: July, 2018 9  pH Source: https://www.growthtechnology.com/growtorial/what-is-the-ph-value/ Last Accessed: July, 2018 Solubility of Specific Ions based on Water pH 10  Alkalinity ‘acid neutralizing capacity'. Important because it buffers the water against changes in pH. For most waters, alkalinity includes the - 2- bicarbonate (HCO3 ) and carbonate (CO3 ) ions. Other ions such as orthophosphates, borates etc. may contribute to alkalinity but in small amounts. 11  Alkalinity Total alkalinity is measured by measuring the amount of acid (e.g., sulfuric acid) needed to bring the sample to a pH of 4.2. At this pH all the alkaline compounds in the sample are "used up." The result is reported as milligrams per liter of calcium carbonate (mg/L CaCO3). 12 Source: https://openi.nlm.nih.gov/detailedresult.php?img=PMC3659369_fpls-04-00140-g005&req=4 Last Accessed: July, 2018  Conductivity Measures electric conductivity (EC) of water Higher value means water is a better electrical conductor Increases when more salt (e.g., sodium chloride) is dissolved in water Indirect measure of salinity Units are μmhos/cm at 25o C or μsiemens/cm Source: http://www.kgs.ku.edu/Publications/Bulletins/260/04_chem.html Last Accessed: July, 2018 Source: http://encyclopedia.che.engin.umich.edu/Pages/ProcessPar ameters/ConductivityMeters/ConductivityMeters.html Last Accessed: July, 2018 13  Salinity Classification of Ground Water Composition Based on Total Dissolved Solids Content Type of Water Dissolved salt content (mg/l) Fresh water < 1,000 mg/l Brackish water 1,000 - 3,000 mg/l Moderatly saline 3,000 - 10,000 mg/l water Highly saline 10,000 - 35,000 mg/l water Sea water > 35,000 mg/l Source: http://www.horiba.com/fileadmin/_migrated/RTE/ RTEmagicC_potassium_sea_water_04.png.png Last Accessed: July, 2018 14  Dissolved Oxygen Amount of gaseous oxygen (O2) dissolved in water Oxygen gets into water by diffusion from the surrounding air, by aeration, and through photosynthesis DO range from 0-14 mg/l Need 5-6 mg/l to support a diverse population DO < 2 mg/l - Hypoxia Source: https://link.springer.com/chapter/10.1007/978-3-319-44234-1_10 Last Accessed: July, 2018 15  Turbidity Measured in Nephelometric Turbidity Units (NTU) Estimates light scattering by suspended particles Photocell set at 90o to the direction of light beam to estimate scattered rather than absorbed light Good correlation with concentration of particles in water Source: https://dec.alaska.gov/water/wqsar/trireview/pdfs/Tri_Review_Turbidity_Fact_Sheet_ 01-08-15.pdf Last Accessed: July, 2018 16  Turbidity A nephelometer measures scattered light at right angles to the source. Pure water Cloudy water Detect Detect light light 17  Solids Turbidity is a visible indicator of the presence of “solids” in a water sample. Solids, as the term is used in water analysis, refers to residue left upon evaporation and may be dissolved or undissolved species. The more common chemical usage would be undissolved material which may include sediment or “suspended material”. Sometimes, water analysis will refer to “dissolved solids” which are determined by evaporating the water and drying the material. 18  Solids Total solids is the combination of all solids. The “total solids” can be determined by evaporation of a water sample and drying of the residue (at 110°C). The mass of remaining solids relative to the volume of water evaporated is the measure. Q. What compounds make up total solids? A. Everything that doesn’t evaporate below 110°C! Examples include: inorganic salts, organic material, insoluble salts, soluble salts, metals etc 19  Solids Solids come in different types: Undissolved solids are responsible for turbidity or sediment. These can be isolated simply by filtering. Dissolved solids are responsible for the hardness of water. Dissolved solids specifically refers to samples isolated by drying at 180°C which removes any bound water. 20  Solids Volatile solids are those solids that will burn off at 550°C or lower. This includes the vast majority of organic compounds. Fixed solids are those remaining after pyrolysis (burning at 550°C) and consist largely of inorganic salts. These salts are most directly related to hardness. Settleable solids refers to those solids that will form sediment if not stirred up. Can be determined by simply allowing the material to sit in an Imhoff cone for an hour. 21  Solids 1 L of waste water is collected. 1 hour settling in an Imhoff cone. The remaining liquid is decanted and filtered using a 1 micron filter (initial weight 2.0460 g), the solid isolated in the Imhoff cone is dried at 110°C and found to weigh 20.0210 g. The filter paper is dried and weighed = 2.1052 g. The remaining liquid is evaporated and dried at 110°C resulting in 1.2375 g of residue. Further drying at 180°C results in 0.9467 g of remaining residue from the evaporation. All three residues were combined and ignited at 550°C, resulting in 6.4547 g of residue. What is the concentration of suspended solids, total solids, total volatile solids, and total dissolved solids? (With appropriate units.) 22  Solids Suspended solids are equally easy to determine, but they SOMETIMES INCLUDE SETTLEABLE SOLIDS (usually for natural systems where time is less limited): Including settleable solids, total suspended = 20.0210 g + (2.1052 g -2.0460 g) = 20.0802 g Suspended solids = 20.0802 g/L = 20,080.2 mg/L 23  Solids Total solids would include everything left after drying at 110 °C (settleable + suspended + dried residue): Total solids mass = 1.2375 g + 20.0802 g = 21.3177 g Total solids = 21.3177 g/L = 21,317.7 mg/L 24  Solids Total dissolved solids are those left after filtering and 180 °C drying (EXCLUDING the suspended/settleable): Total dissolved solids = 0.9467 g = 0.9467 g/1 L = 946.7 mg/L 25  Solids  Total solids = 21.3177 g/L = 21,317.7 mg/L  Total fixed solids = 6.4547 g/1 L = 6,454.7 mg/L  Total volatile solids = 14.8630 g/1 L = 14,863.0 mg/L  Total suspended solids = 20,080.2 mg/L  Total dissolved solids = 946.7 mg/L 26  Dissolved Constituents Major Constituents (> 5 mg/L) – Ca – Mg – Na – Cl – Si – SO42- - sulfate – H2CO3 - carbonic acid – HCO3- - bicarbonate 27  Dissolved Constituents Minor Constituents (0.1 - 5 mg/L) – B – K – F – Sr – Fe – CO32- - carbonate – NO3- - nitrate 28  Dissolved Constituents Trace Constituents (< 0.1 mg/l) – Al – Pb – As – Mn – Ba – Ni – Br – Se – Cd – Ag – Co – Zn – Cu – others 29  Water Classification How? – Compare ions with ions using chemical equivalence – Making sure anions and cations balance – Use of diagrams and models Why? – Helps define origin of the water – Indicates residence time in the aquifer – Aids in defining the hydrogeology – Defines suitability 30  Chemical Equivalence Chemical analysis of water samples – Concentrations of ions are reported by weight (mg/L) chemical equivalence (meq/L) Takes into account ionic charge Equivalent Concentration 31 Source: https://ptable.com/ Last Accessed: July, 2018  Chemical Equivalence Going from mg/L (ppm) mmoles/L meq/L for ion X __ mg X 1 mmole X Z meq X = __ meq/L of X 1 L ATW mg X 1 mmoles X Where: ATW = the atomic weight of the ion from the periodic table. Z = the absolute value of the charge of the ion. 33 Courtesy: F E Harvey, University of Nebraska  Chemical Equivalence For a 10 mg L-1 solution of Sodium: Na+ 10 mg Na 1 mmole Na 1 meq Na = 0.4 meq/L Na 1 L 23 mg Na 1 mmole Na Where: ATW is the atomic weight of sodium = 23. Z is the absolute value of the charge of the ion = 1. 34 Courtesy: F E Harvey, University of Nebraska  Chemical Equivalence For a 10 mg L-1 solution of Sulfate: SO42- 10 mg SO4 1 mmole SO4 2 meq SO4 = 0.2 meq/L SO4 1L 96 mg SO4 1 mmole SO4 Where: ATW is the atomic weight of sulfate = 96 Z is the absolute value of the charge of sulfate = 2. 35 Courtesy: F E Harvey, University of Nebraska  Chemical Equivalence If all ions are correctly determined by a lab – sum of cations should equal sum of anions (all in meq/L) Errors in analysis and chemical reactions in samples – 5% difference is considered acceptable – > 5%, question the lab results 36  Chemical Equivalence Sandstone Aquifer Parameter Example: mg/L meq/L Na+ 19 0.827 The atomic wt. of Sodium Cl- 13 0.367 (valence of one) = 22.989 SO4 2- 7 0.146 and its charge is one Ca2+ 88 4.391 Dividing the concentration of Mg2+ 7.3 0.6 sodium in the sample (19 mg/L) HCO3 - 320 5.245 by its “combining wt.” = 0.827 meq/L or its equivalent Total Anions 5.758 concentration. Total 5.818 Cations % 1% Difference 37  Chemical Equivalence There numerous types of diagrams on which anions and cations (in meq/L) can be plotted. These include: – Piper – Stiff – Pie – Depth Profile 38  Piper Diagrams Two ternary diagrams Projected on quadralinear diagram Very useful figure for comparing concentrations of numerous water samples Convert concentrations to meq/L Calculate %’s of each element on ternary diagram Plot %’s on ternary diagrams Courtesy: F E Harvey, University of Nebraska Project each % onto diamond diagrams Courtesy: F E Harvey, University of Nebraska  Piper Diagram All values are in mg/L Water Ca Mg Na K HCO3 SO4 Cl 1 83 24 95 5.0 135 270 82 1. Convert the data in the table above to meq/L using the previously provided formula. Water Ca Mg Na K HCO3 SO4 Cl 1 4.14 1.97 4.13 0.13 2.21 5.62 2.31 Cations (+ charged) Anions (- charged) 40 Courtesy: F E Harvey, University of Nebraska  Piper Diagram Water Ca Mg Na K HCO3 SO4 Cl 1 4.14 1.97 4.13 0.13 2.21 5.62 2.31 2. Normalize each value to the total by dividing each value by the total X 100 percent. (Remember to combine Na and K) Total Cations = 10.37 Total Anions = 10.14 Charges should balance so these should be close Water Ca Mg Na + K HCO3 SO4 Cl 1 40 19 41 22 55 23 = (4.14/10.37)*100 = 39.92 = 40 Must add up to 100% Must add up to 100% 41 Courtesy: F E Harvey, University of Nebraska  Piper Diagram 3. Plot the normalized 80 80 Ca lciu 60 values on the piper ) (Cl m(C ride a)+ 60 diagram by plotting hlo Ma 40 )+C 120,000 150,000 30,000 60,000 90,000 gn O4 cations on the left, esi 0 e(S 40 um Total Dissolved Solids lfat (Mg anions on the right, Su (PartsPer Million) ) 20 20 and then projecting up into the diamond. Mg SO 4 20 20 4. Classify each water ) O3 So 20 80 80 20 (HC 40 using the Classification on 40 diu ate m( 40 g) Na (M Su System arb 60 60 40 )+P um 60 lfat 3)+ 60 Bic esi ota 60 e(S 40 gn ssi O4 CO Ma um 60 ) 40 te( 80 (K) rbo 80 na Ca 80 20 20 80 Ca 80 60 40 20 Na+K HCO +CO 3 3 20 40 60 80 Cl Calcium (Ca) Chloride (Cl) C A T I ON S %meq/l A NI O NS 42 Courtesy: F E Harvey, University of Nebraska  Stiff Diagrams Concentrations of cations are plotted to the left of the vertical axis and anions are plotted to the right (meq/L). The points are connected to form a polygon. Waters of similar quality have distinctive shapes. Source: http://www.kgs.ku.edu/General/Geology/Ellsworth/05_gw.html Last Accessed: July, 2018 43 Pie Diagrams Source: https://pubs.usgs.gov/ha/ha730/ch_g/G- Appalachian_Plateaus5.html Last Accessed: July, 2018 44  Pie Diagrams Parameter Sea water Example River (mg/L) water (mg/L) Na 10,500 20 Cl 19,000 24 SO4 2,700 51 Ca 410 38 Mg 390 10 HCO3 142 113 45 Courtesy: Daene C. McKinney, University of Texas  Groundwater Quality Parameter Sandstone Limestone Igneous/ Shale with Alluvium Aquifer Aquifer Volcanic Salts (Farmland) Aquifer pH 7.5 7.8 6.5 7.1 7.4 Na 19 29 184 1220 114 Cl 13 53 6 1980 30 SO4 7 60 7 1000 74 Ca 88 144 34 353 64 Mg 7.3 55 242 159 19 HCO3 320 622 1,300 355 402 NO3 0.4 0.3 0.2 2.4 60 46  Hardness Hardness in water is typically defined as the presence of divalent cations (Be+2, Mg+2, Ca+2, Sr+2, Ba+2 & Ra+2). Hardness causes water to form scales and a resistance to soap. ‘Hard’ water doesn’t produce lather with soap solutions, but instead produces white precipitate. 47 Courtesy: F E Harvey, University of Nebraska Hardness Source: http://www.waterfyi.com/featured/hard- water-scale-solutions/ Last Accessed: July, 2018 48  Hardness Hardness in most natural waters is caused primarily by compounds of calcium (Ca+2) and magnesium (Mg+2). Can be classified as carbonate hardness (Ca(HCO3)2, Mg(HCO3)2, CaCO3, and MgCO3) or noncarbonate hardness (CaCl2, MgSO4, and MgCl2). Total hardness is the sum of carbonate and noncarbonate hardness. Variety of other metals at lesser concentrations can also contribute to the total hardness. 49  Hardness Methods of Determination 1. Complete Cation Analysis – Most accurate – Calculation of the hardness caused by each divalent cation is performed by use of the general formula: Hardness (mg/L) as CaCO3 = M2+(mg/L) X 50 EW of M2+ where M2+ represents any divalent metallic ion and EW represents its equivalent weight 50  Hardness Example Calculate the hardness (in mg/L as CaCO3) of a water sample with the following analysis: Cation Concentration Anion Concentration (mg/L) (mg/L) Na+ 20 Cl- 40 Ca2+ 15 SO42- 16 Mg2+ 10 NO3- 1 Sr2+ 2 Alkalinity 50 51  Hardness Example Cation EW Hardness, mg/L as CaCO3 Ca2+ 20.0 (15)(50)/(20.0) = 37.5 Mg2+ 12.2 (10)(50)/(12.2) = 41.0 Sr2+ 43.8 (2)(50)/(43.8) = 2.3 Total hardness = 80.8 52  Hardness 2. Titrimetric Method – The titration method is based on a colorimetric reaction that occurs when all hardness ions have been removed from the solution. – Initially, the pH of the sample is adjusted to >10 using an ammonium hydroxide-ammonium chloride buffer. Next, an indicator solution (Eriochrome Black T or calmagite) is added. – Ethylenediaminetetraacetic acid (EDTA) is titrated into the sample until a colour change occurs. – When all of the Ca++ and Mg++ have been removed by EDTA, the dye changes from wine-red to blue. 53  Hardness 2. Titrimetric Method Source: https://chem.libretexts.org/Demos%2C_Techniques%2C_and_Experiments/General_Lab_Techniques/Titration/Complexation_Titration Last Accessed: July, 2018 End point for the titration of hardness with EDTA using calmagite as an indicator; the indicator is: (a) red prior to the end point due to the presence of the Mg2+– indicator complex; (b) purple at the titration’s end point; and (c) blue after the end point due to the presence of uncomplexed indicator. 54  Alkalinity and Hardness So, if Alkalinity is mostly bicarbonate and carbonate… And, Hardness is mostly calcium and magnesium… End result is that these variables largely track each other under most conditions in nature 55  Alkalinity and Hardness An analysis of a sample of water results in the following: alkalinity = 220 mg/L; hardness = 180 mg/L; Ca2+ = 140 mg/L; OH-, insignificant. All concentrations are expressed as CaCO3. (a) what is the noncarbonated hardness? (b) What is the Mg2+ content in mg/L? 56  Temperature − Optimum temperature for drinking water is around 10 - 15°C. − DO concentrations are more in colder water. − At higher temperatures, the rate of biological activity is higher if organics are present in water. − Temperature affects various treatment processes, especially during wastewater treatment. Landsat image of Lake Trawsfyndd, Wales illustrating color differentiation of temperature differences induced by power plant thermal pollution. Source: NASA Source: http://www.trunity.net/hendricks_rtaylor/view/article/51cbef117896bb431f69c24b/ Last Accessed: July, 2018 57  Taste and Odor − Important aesthetic parameters. − Can also indicate contamination as these are the indicators of organics and inorganic compounds. − Odor is measured in terms of the Threshold Odor Number (TON). − TON is the ratio by which sample has to be diluted for the odor to become undetectable to human nose. − TON = (Volume of sample + Volume of pure water added to make the sample odor free) / Volume of sample − TON should be 1 for public water supplies. 58  ENVENG 200 Fundamentals of Environmental Engineering Dr. Lokesh P. Padhye Water Quality  Class Objectives Understand the water quality parameters Understand their measurement and standards Understand the mass balance 2  Pathogens in Water History Introduction & Overview Pathogenic Bacteria, Viruses, and Protozoa Methods Regulations & Standards Escherichia coli Scanning electron micrograph Source: https://fineartamerica.com/featured/12-e-coli-bacteria-sem-steve-gschmeissner.html Last Accessed July 2018 3  Pathogens in Water History The determination of water-borne pathogens as the causative factor in an outbreak uses the classical detective work of epidemiological studies. In 1854, a cholera outbreak in London, England was shown by a physician, John Snow, to be linked to a pump that derived its water from a polluted section of the River Thames. People served by a pump that obtained its water upstream of London had a low incidence of cholera. In 1847, physician William Budd showed that there was an association between typhoid fever in a street in Bristol, England and the use of a particular drinking water well. People on an alternate water supply did not become infected. This was decades before the causative agent for typhoid was identified. The appreciation of water as a carrier of disease-producing organisms only came about in the mid-1860's with the firm establishment of the germ theory by Pasteur and Koch. 4  Pathogens in Water Epidemiology and Cholera What is cholera?...all is darkness and confusion, vague theory, and a vain speculation. Is it a fungus, an insect, a miasma, an electrical disturbance, a deficiency of ozone, a morbid off-scouring from the intestinal canal? We know nothing; we are at sea in a whirlpool of conjecture. - Wakley T. The Lancet II, 393, 1853 Vibrio cholerae Scanning electron micrograph Source: http://remf.dartmouth.edu/Cholera_SEM/ 5 Last Accessed July 2018 Pathogens in Water Cholera is still here 6  Pathogens in Water General Characteristics Most water-borne pathogens may be classified as viruses, bacteria, or protozoa. They typically cause intestinal diseases, leaving the host in the fecal material, contaminating the water supply, and then entering the recipient by ingestion. Their survival period in water varies widely and is influenced by many factors such as salinity, temperature, etc. It may be generalized that cellular viruses last longer than bacteria while protozoa can extend their survival time by encystation. 7  Pathogens in Water Viruses Although there are over 100 known water-borne human enteric viruses, infectious hepatitis A, poliovirus and viral gastroenteritis are of practical concern as water-borne viruses. Tests for the presence of viruses in water supplies are difficult and uncertain and so little is known of the survival time and concentration distribution of viruses in water sources. In general, enteric viruses survive less than three months in the environment but have been reported surviving up to five months in sewage. There is dispute over whether a minimum infectious dose is necessary as for viruses, some researchers claiming that a single virus is sufficient for infection. 8  Pathogens in Water Bacteria Bacteria comprise the largest group of water-borne pathogens. A minimum infectious dose of several hundred to several thousand organisms is necessary to cause bacteriological infection. Low temperatures, sediment adsorption, and anoxic conditions occasionally prolong their survival. The most common bacteriological diseases are: Shigella sp., the cause of dysentery, is almost strictly a human affliction (minor in other primates). Salmonellosis sp. cause gastrointestinal diseases, while one variety, which is strictly a human pathogen, causes typhoid. Cholera is a serious, highly contagious disease causing dramatic and fatal loss of water and electrolytes. Healthy carriers may make up 1-9% or even up to 25% of the population. 9  Pathogens in Water Protozoa Protozoans entering the host body by ingestion are usually in cyst form. Protozoans of major concern as water-borne pathogens are Giardia, Cryptosporidium, and Entamoeba. One to ten cysts of the flagellated Giardia is the minimal infection dose and causes serious diarrhea. Source: https://www.blatner.com/adam/consctransf/potpourri/6-protozoa/6-Protozoa.html Last Accessed: July, 2018 10  Pathogens in Water Indicator Organisms The concept of an indicator organism is used to indicate the possible presence of disease-causing constituents. Such an indicator organism should behave as follows: − be applicable to all water − be present when pathogens are − have no aftergrowth in water − be absent when pathogens are − have constant characteristics − persist longer than pathogens − be harmless to humans − correlate quantitatively with pathogens − be present in greater numbers than pathogens − be easily, accurately and quickly detected. 11  Pathogens in Water Escherichia coli as indicator organisms The coliform group nearly fulfills the criteria listed above. Escherichia coli is considered a reliable indicator of bacterial pathogens. Protozoans and viruses, however, usually survive longer than E. coli and may also survive disinfection which is otherwise adequate for bacteria. Filtration is usually successful in extracting protozoans and viruses and should be used in conjunction with disinfection procedures. 12  Pathogens in Water Total coliforms – All members of the total coliform group can occur in human feces, but some can also be present in animal manure, soil, and submerged wood and in other places outside the human body. Indicator for drinking water only. Fecal coliforms – A subset of total coliform bacteria, more fecal-specific in origin, but also present in textile and pulp and paper mill wastes. Source: http://www.sciencephoto.com/set/3194/bacteria-images-dennis-kunkel Last Accessed: July, 2018 E. coli - Specific to fecal material from humans and other warm- blooded animal. EPA recommended best indicator for recreational waters 13  Pathogens in Water Most Probable Number It is based upon the application of the theory of probability to the numbers of observed positive growth responses to a standard dilution series of sample inoculum placed into a set number of culture media tubes. Coliforms identified by gas production Refer to tables and determine statistical range of number of coliforms Does not: Detect total number of bacteria Specific pathogens 14  Pathogens in Water Typical Water Quality Standards Drinking Water – No coliforms contamination acceptable Recreational water – 200 fecal coliforms /100 ml Fish and wildlife habitat – 5,000 fecal coliforms/100 ml Shellfish – 14 fecal coliforms/100 ml 15  Pathogens in Water Direct Tests For Pathogens Involves selective cultivation to large numbers – Time consuming – Expensive – Potentially dangerous to lab personnel Molecular tests – Require testing for each pathogen – Expensive – Require expertise 16  Pathogens in Water Virus Detection Very difficult and costly Electron microscopy Immunoassays Cell cultures Reverse transcription-polymerase chain reaction (RT- PCR) 17  Iron One of the earth’s most plentiful resource High iron causes brown or yellow staining of laundry, household fixtures Metallic taste, offensive odor, poor tasting coffee MAV for NZ – 0.2 mg/L Secondary Maximum Contaminant Level (MCL) – 0.3 mg/L 18  Chloride High chloride in water caused by - dissolution of salt deposits - contamination by wastewater effluent - intrusion of sea water Not harmful to human beings Most troublesome anion for irrigation MAV for NZ and Secondary MCL - 250 mg/l 19  Nitrate Increasing level of nitrate in source water due to agricultural fertilizers, manure, animal waste, nitrogenous material, sewage pollution Causes blue baby syndrome (methaemoglobinaemia) in infants MAV – 11.3 mg/L MCL – 10 mg/L 20  Fluoride Occurs naturally or can be added during the water treatment Long term consumption above permissible level can cause – dental fluorosis (molting of teeth) Skeletal fluorosis Secondary MCL – 2 mg/L 21  Arsenic Occur in ground water naturally in some regions or can be a source from industrial waste or agricultural insecticide High arsenic causes various type of dermatological lesions, muscular weakness, paralysis of lower limbs; can also cause skin and lung cancer MAV and MCL – 0.01 mg/L 22  Heavy Metals Present as mineral in soil and rocks of earth Common Human activities Battery – Lead & Nickel Textile – Copper Photography – Silver Steel production – Iron Can bioaccumulate in body to cause chronic toxicity 23  Emerging Contaminants PPCPs, Pesticides, Herbicides, Disinfection Byproducts, Other Organics…… Various sources – almost all anthropogenic Can cause cancer, birth defects, blood disorder, nervous disorder, genetic damage 24  NZDWS NZDWS 2005 Maximum Test Typical Range Comment Acceptable Value (MAV) Surface water that is low in pH can attack copper piping leading to high levels of pH 5.5 - 7.5 7.0 - 8.5 (Guideline Value) dissolved copper Important for ion balance check and other parameter estimation. Used to calculate Conductivity NA