• Alkalinity (bicarbonate) compounds • Ammonia, nitrite, nitrate • Pesticides • Chloride • Fats and oils • Metals • Detergents Inorganics in groundwater Dissolution: Example-Calcium carbonate dissolution to calcium ion and bicarbonate ion
CaCO3(s) + H 2 0 Ca 2+ + HCO 3− + OH − Oxidation-reduction: change in oxidation state. Example-reduction of ferric iron in low oxygen water 3+ − 2+ Fe + e → Fe Ion exchange: interaction between negatively charged clay particle in sediment and cation in solution. Example: sodium ion exchange with potassium to produce mineral Albite
KAlSi3O8 (s) + Na + → NaAlSi3O8 (s) + K +
Complexation: reaction of organic compound with waters in high ionic
concentration pH
• pH is a measure of the concentration
of hydrogen ions (H+) in water • Negative log of hydrogen ion conc. • pH ranges from 0 to 14 – 7 neutral – 0 - 7 acidic – 7 - 14 alkaline • Standard range (between 6.5-8.5)
Acid release H+ ion in water
Bases accept H+ in ion water pH = -log10[H+] Hardness • Hard water is water that contains cations with a charge of +2, especially Ca2+ and Mg2+ • These ions leave insoluble mineral deposits • To "soften" hard water; remove the calcium and magnesium ions • Units of mg/L as CaCO3 • Soft water 0-50 mg/L as CaCO3 • Hard water 100-150 mg/L as CaCO3 Carbonate and non-carbonate hardness
Hardness = (Ca 2+ ) + (Mg 2+ )
• Carbonate hardness causes the scale formation –
CaCO3 precipitation
• Non-carbonate hardness associated with other
anions, particularly Cl- and SO42- Carbon-dioxide gas • Carbon-dioxide gas enters water from atmosphere and as a by- product of respiration and microbial decay of natural organic matter CO 2 (atmosphere) CO 2 (water)
(CO 2 ) aq + H 2 O H 2 CO 3 − + CO 2 + H 2 O HCO + H 3 − 2− + HCO CO + H 3 3 Alkalinity • Alkalinity refers to the capability of water to neutralize acid (accept H+ ions) • Buffering capacity or ability of water to resist changes in pH
• A buffer - a solution to which an acid can be added
without changing the concentration of available H+ ions (pH) appreciably. • Primary source of alkalinity is the carbonate system • For most waters, alkalinity includes the bicarbonate ion (HCO3-) • Nitrogen is an essential Nitrogen compounds component of proteins and nucleic acids • Atmosphere is 78% nitrogen gas
8 Inc. All rights reserved. Nitrogen • Most sources of nitrogen are biological origin and atmospheric nitrogen • Most important forms are: ammonia (NH3, -III), ammonium (NH4+, -III), nitrogen gas (N2, 0), nitrite ion (NO2-, +III), nitrate ion (NO3-, +V) • Total nitrogen: organic nitrogen, ammonia, nitrite and nitrate • Organic fraction is a mixture of compounds as amino acids, amino sugars, and proteins, can be soluble or particulate • Decomposition of bacteria changes organic form to ammonia • In aerobic environment the ammonia is further oxidizes to nitrite and nitrate
Total Kjeldahl nitrogen (TKN) is total of organic nitrogen and ammonia Nitrogen
• Nitrite is unstable easily oxidizes to nitrate
• Nitrate is fetal to infants and is regulated when wastewater reclaimed for groundwater recharge (0-20 mg/L as N) • Nitrate was present in shallow and deep aquifers • High nitrate concentration show a clear impact of human activity as use of pesticides and fertilizers and wastewater contamination Chlorides • Chlorides in natural waters result from chloride-containing rocks which water comes in contact • In addition agriculture, domestic and industrial WW are a source • Human excreta contain 6 gr of chlorides per day • Conventional WWTP do not remove chlorides significantly • It impacts final reuse application of treated WW and surface groundwater contamination with wastewater • At the Mezquital Valley aquifer, average chloride of 162 mg/L (Lesser, 2013), below permissible limits (250 mg/L) Metals • A substance with high electrical conductivity, luster, which readily loses electrons to form positive ions (cations). • Metals are otherwise defined according to their position on the Periodic Table, including groupings as alkali metals, alkaline earth metals, transition metals, and rare earth metals.
academic.emporia.edu Metals
• Trace quantities of many metals such as nickel,
manganese, lead, chromium, copper, cadmium, zinc, iron, and mercury are present in most waters • The presence of any of these metals in excessive quantities will interfere with the beneficial uses of the water due to toxicity Metals • High metal conc. suggest irrigation with excess domestic and industrial wastewater • In addition, low solubility of oxygen (negative redox) and high temperatures, may facilitate metal oxide mobilization (as iron and manganese) from the soil to groundwater • Arsenic is unique as it is found at typical groundwater pH values and under both oxidizing and reducing conditions. • Arsenic may be of natural origin and industrial pollution Important chemical parameters : Inorganics Organics
• semi-Volatile organic • Alkalinity (bicarbonate) compounds • Ammonia, nitrite, nitrate • Pesticides • Chloride • Fats and oils • Metals • Detergents Organic chemical constituents • Organic – a class of chemicals composed of carbon (C), hydrogen (H) and in some cases oxygen (O) with nitrogen (N). Can also contain sulfur (S), phosphorus (P), and halogens as chlorine (Cl), bromine (Br) and Iodine (I)
By heating or mixing the water sugar dissolution is
accelerated • Oil cannot create enough “Van der-Waals” bonds with water and will not be dissolved
Olive Oil Vegetable Oil
Sources of organics in water 1. Natural organic matter (NOM) – chemical and microbial degradation of vegetation and soil material 2. Compounds from human activities – wastewater contamination 3. Disinfection by-products 4. Formed/added during treatment Natural Organic Matter (NOM) • Organic matter originating from plants and animals present in natural (untreated or raw) waters, for example, in lakes, rivers and reservoirs. • In order to minimize water disinfectant byproducts, NOM should be removed from waters to be treated with a disinfectant.
• Measured by total organic carbon (TOC) as a surrogate
measure or by dissolved organic carbon (DOC). Organic matter in wastewater • Proteins (40-60%) • Carbohydrates (25-50%) • Fats, oils, and grease (8-12%) • Urea – major constituent of urine only in very fresh WW • Along with the above also small quantities of a very large number of synthetic organic compounds, with simple to complex structure Total organic carbon (TOC) • TOC test is used to measure the organic matter present in water • The test is performed by injecting a known quantity of sample into a high temp. furnace (and oxygen) or chemically-oxidizing environment • The carbon dioxide produced is measured quantitatively • Dissolved organic carbon (DOC) is the fraction of TOC that passes an 0.45m filter • Relatively fast analysis At the Mezquital Valley aquifer, average DOC and TOC of 4.2 and 19.1 mg/L (Lesser, 2013), no permissible limits Nevertheless these are high conc. Individual organic compounds • Requires sophisticated instruments for measuring trace concentrations in the range of 10-12-10-3 mg/L such as gas chromatograph and liquid chromatographic methods Classification of Organic Pollutants (adapted from WHO) Volatile Organic Compounds (VOCs) • Very volatile: compounds that have low boiling points, usually less than < 1000C, and therefore evaporate readily. Some are gases at room temperature. • Volatile: boiling points less than 2500C. • VOCs are ground-water contaminants of concern because of very large environmental releases, human toxicity, and a tendency for some compounds to persist in and migrate with ground-water to drinking-water supply well • VOC’s include Methyl-tert-Butyl Ether (MTBE) , Tri-Halo- Methanes (THMs), benzene, toluene, ethylbenzene xylen (BTEX) and Tert-Butyl-Acetate (TBA) Sources of contamination • Groundwater contamination with Volatile Organic Compounds are due to leaking underground fuel or solvent storage vessels, agriculture practices and wastewater disposal
• Storage tanks • Septic systems • Landfills • Chemicals Methyl tertiary-butyl ether (MTBE) • MTBE is used as a fuel additive in motor gasoline and produced in very large quantities. • It is one of a group of chemicals known as "oxygenates" because they raise the oxygen content of gasoline. • At room temperature, MTBE is a volatile, flammable and colorless liquid • MTBE is found in ground water; that may be sources of drinking water. • MTBE dissolves easily in water therefore rapidly migrates in groundwater, and is persistent. • Low levels of MTBE can make drinking water supplies undrinkable due to its offensive taste and odor. http://archive.epa.gov/mtbe/web/html/water.html Trihalomethanes (THM) • Produced during chlorination of water containing organics – may form compound that are potentially human carcinogens • Normally found THMs are chloroform (CHCl3), bromodichloromethane (CHBrCl2), dibromochloromethane (CHBr2Cl) and bromoform (CHBr3) BTEX • BTEX is the term used for benzene, toluene, ethylbenzene, and xylene-volatile aromatic compounds typically found in petroleum product, such as gasoline and diesel fuel • Present in coal tar, petroleum products, and various organic chemical product formulations • At the Mezquital Valley aquifer, toluene was detected at an average conc. of 10.3 mg/L, higher than the permissible limit of 0.7-1.0 mg/L (Lesser, 2013) • These are the most soluble of the major gasoline compounds and, therefore, are common indicators of gasoline contamination of groundwater
http://toxics.usgs.gov/definitions/btex.html Semi-Volatile Organic Compounds • Organic compound which has a boiling point higher than water • They may vaporize at temperatures above room temperature • Moderate tendency to volatilize sVOC’s include: • Diesel Range Origin C10-C28 (DRO) • Gasoline Range Origin C4-C10 (GRO) • Oil Range Origin C28-C40 (ORO) • Polyaromatic Hydrocarbons (PAH), Phenols, Pesticides Hydrocarbons, particularly alkylbenzenes may give rise to a very unpleasant “diesel-like” odor (WHO, 2012) http://www.epa.gov/reg3hwmd/bf-lr/regional/analytical/semi-volatile.htm Pesticides • A pesticide is any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest • Pests are living organisms that occur where they are not wanted or cause damage to crops or humans or other animals. Include: insects, mice, unwanted plants (weeds), fungi and microorganisms. • Examples of pesticides: Alachlor, Aldicarb, Atrazine, Diuron, Malathion, Methyl parathion, Metolachlor • Pesticide contamination of groundwater especially in agricultural areas http://water.usgs.gov/edu/pesticidesgw.html
http://www.epa.gov/pesticides/regulating/index.htm#review Pesticide DDT (dichlorodiphen- yltrichloroethane) A comparison of the number of successful bald eagle • Banned in the US in 1972 offspring with the level of DDT residues in their eggs.
• Causes birds to lay eggs with thin
shells, break during incubation • Persistence, bioaccumulation, Biological magnification
http://www.atsdr.cdc.gov/toxprofiles/tp123-c3.pdf Total Fat ,Oil and Grease (Grasas y Aceites) • Specific contaminants that are components of Total Petroleum Hydrocarbons, such as BTEX (benzene, toluene, ethylbenzene, and xylene), n-hexane, jet fuels, automative gasoline, fuel oils, and mineral oil including mineral-based crankcase oil • Automotive gasoline typically contains about 150 hydrocarbon compound • The exact composition of petroleum products varies depending upon (1) the source of the crude oil (crude oil is derived from underground reservoirs which vary greatly in their chemical composition) and (2) the refining practices used to produce the product. • During the refining process, crude oil is separated into fractions having similar boiling points. http://www.atsdr.cdc.gov/toxprofiles/tp123-c3.pdf Detergents • Detergents include Anionic, Cationic and non- anionic. • Usually only anionic detergent is to be determined in ground water. • Anionic- extraction with chloroform, thereafter, methylene blue is used for a color reaction (MBAS method) • At the Mezquital Valley aquifer, MBAS parameter was detected at an average conc. of 0.7 mg/L (max 20.50), higher than the permissible limit of 0.5 mg/L (Lesser, 2013)
