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Outline – Major WQ Indicators "The noblest of the elements is water" Pindar, 476 B.C. What’s in the Water? Surface water quality ADEQ SW Short Course June 13, 2013 Phoenix, AZ Turbidity Dissolved Oxygen & Temperature pH Salinity Nutrients Organic substances (Biological Oxygen Demand) Inorganic substances (metals, sediments, nitrates, water hardness) Toxics Micro‐organisms AZ Water Quality Standards Slides Thanks to: J. McIntosh UA-HWR (2012) Water: What it is; Why it is a good solvent? Bottom line: one‐page summary • • • • • • • • Water is a universal solvent DO inversely related to water temperature Salinity affects taste and corrosivity Nitrate source is Ag runoff Pesticides can bio accumulate bacteria source is human and animal waste Inorganic contamination is rare Emerging contaminants are ubiquitous but low conc. SO42Ca2+ Water is a colorless, odorless liquid by itself – it is contaminants that give it taste Chemical bonding of the water molecule makes it a good solvent - polar compound - can attach to positive and negatively charged molecules Vigil, Kenneth M..; Clean Water : An Introduction to Water Quality and Water Pollution Control (2003) J. McIntosh UA-HWR (2012) Why is water a good solvent? Almost all solids, liquids, and gases placed in water will dissolve to some extent Concentrations (mg/L) San Pedro Basin AZ, GW silica (Si) Valles Caldera NM, SW Sea Water 16.0 As water passes over rocks, or through soils and bedrock, it can dissolve minerals, picking up dissolved constituents (e.g. Ca, Fe, K, Na, Cl, SO4) sodium (Na) 12.3 7.3 calcium (Ca) 51.5 5.9 420 magnesium (Mg) 4.2 1.1 1,300 bicarbonate (HCO3) 171 9.0 145 Some of the substances dissolved in water, or transported by water, can lower its water quality (e.g. arsenic, lead, nitrates, E Coli), while some substances improve water quality (e.g. oxygen) chloride (Cl) 5.5 1.7 19,250 sulfate (SO4) 5.0 1.7 2,700 TDS 250 43 35,000 Vigil, Kenneth M..; Clean Water : An Introduction to Water Quality and Water Pollution Control (2003) J. McIntosh UA-HWR (2012) Major Ion Chemistry of Different Water Types? 10,700 Units: Parts per million (ppm) – think of a container filled with a million marbles of equal size and weight. If a reported value (of arsenic for example) is 10 ppm, then 10 out of 1 million marbles are arsenic atoms, while the rest of the marbles are water. In most cases…ppm = mg/L …because for water, 1 mg ~ 1 mL, so 1 mg/L = 1 mL/L = 1:1,000,000 Turbidity Dissolved Oxygen & Temperature Measurement of how cloudy the water is (aka, sediment load) Fish and most other aquatic organisms need oxygen to survive. They use oxygen for respiration, just like humans. Turbidity can harm fish, as it reduces visibility and can be abrasive to their gills Most cold water fish (e.g. trout and salmon) prefer ~8-12 ppm of dissolved oxygen (DO), and temperatures from ~34 to 59 oF. How do we measure turbidity? (1) Total suspended solids (TSS) - collect any solid materials on filter paper and weigh. Would you expect DO to be higher or lower in cold water? (2) Total dissolved solids (TDS) - after filtering water sample, and drying, determine how much solid material remains? Oxygen is more soluble in colder water. If you added 500 mg of salt and 500 mg of pepper to 1L of water, what would the TSS and TDS values be? Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) Dissolved Oxygen & Temperature Dissolved Oxygen & Temperature Industrial discharge to surface waters typically needs to be cooled… Fast flowing rivers - typically contain more dissolved oxygen; riffles/whitewater stretches help increase DO. Slow flowing rivers - stagnant waters typically contain lower DO because they don’t rapidly mix with the air along their course Leaving trees around streams during clear cutting to enhance shading. Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) pH Salinity pH = -log (aH+) Definition of salinity: “Saltiness of the water” neutral implies a (aH+) of 10-7 or 1:10,000,000 pH standards of 4 and 10 are a thousand times more concentrated or dilute than pH 7.0 Grams of salt (sum of cations and anions) per kg of solution Salinity ~ Total Dissolved Solids (TDS) Most natural streams Wastewater that is acidic or basic must be treated before being discharged to streams Acid mine drainage; sulfur hot springs J. McIntosh UA-HWR (2012) Vigil (2003) Clean Water Anning (2008) J. McIntosh UA-HWR (2012) Total Dissolved Solids (TDS) >50,000 mg/L Sources of salinity in the environment (~450,000 mg/L most saline water on earth) (1) Seawater intrusion 30,000 to 50,000 mg/L (seawater is ~35,000 mg/L) (2) Saline groundwater in basin-fill aquifers of the SW US: a) b) c) 500 to 30,000 mg/L Natural brines Dissolution of salt deposits Geothermal waters Salinity generally increases with depth and distance from recharge areas <500 mg/L J. McIntosh UA-HWR (2012) J. McIntosh UA-HWR (2012) (3) Agricultural Return Flows (4) Urban runoff Irrigation waters leach salts from soils (mostly from fertilizers); soil waters are typically drained to keep the water table below the root zone; “agricultural runoff” water discharged to local rivers increases salinities ucanr.org High salinities bad for crops - Stunts growth and limits crop yields cleanwatermn.org Salinity issues in the Colorado River Basin Sources of salinity? Agricultural return flows Salt dissolution in geologic formations Natural brine discharge • Clean Water Act & WQ commitments to MX require lower salinities. • $45 million spent every year on salinity management in the CRB • Salt load to Lake Powell has dropped to ~ 7 million tons annually, with a reduction in TDS to Lower Basin users by 125 mg/L, due mostly to better irrigation strategies • $376 million a year in damages to crop reduction, corrosion to household plumping, etc. • For each mg/L in salt reduction = damages reduced by $1.4 million. J. McIntosh UA-HWR (2012) J. McIntosh UA-HWR (2012) Quality of Water, Colorado River Basin, Progress Report #23 - 2011, USBR Salinity of Central Arizona Project (CAP) water near Tucson Nitrate contamination EPA recommended level of TDS for drinking water: 500 mg/L ~650 TW Taste test: Salt tastes bad. Customers prefer a blend of CAP and local ground water in the range of 350 to 450 ppm TDS. Tucson Water is committed to meeting this standard … for now Nitrate (NO3) = most stable form of N in environment, in addition to N2(g), and is highly soluble #1 Water Quality problem in the U.S. Major sources of NO3 contamination 1) N-based fertilizers 2) Animal manure 3) Leaky septic tanks 4) Effluent from wastewater treatment plants 5) Atmospheric Deposition 6) Geologic sources J. McIntosh UA-HWR (2012) Health effects of nitrate contamination J. McIntosh UA-HWR (2012) How is NO3 removed from the environment? (1) Dilution - by mixing with low nitrate waters (e.g. old groundwater, or heavy precipitation) Nitrate in watersheds: Straight from soils to streams? (Sudduth, 2013 J. McIntosh UA-HWR (2012) (2) Denitrification in anoxic environments microbes degrade nitrate J. McIntosh UA-HWR (2012) (1) Nitrogen-based fertilizers “Infants below six months who drink water containing nitrate in excess of the maximum contaminant level (MCL) could become seriously ill and, if untreated, may die. Symptoms include shortness of breath and blue baby syndrome.” (epa.gov) Doctors noticed that babies with “blue baby syndrome” developed symptoms after leaving the hospital, and were not from families using municipal water supplies or being breast feed. Disease linked to babies from rural communities using well water to mix with baby formula. Very few cases reported in the US today, likely because of public education. MCL = 45 mg/L nitrate (NO3) = 10 mg/L nitrate as nitrogen (NO3-N) < 3 mg/L NO3-N uncontaminated groundwater 3-10 mg/L NO3-N likely influenced by human activity >10 mg/L NO3-N highly contaminated groundwater J. McIntosh UA-HWR (2012) Native prairie vegetation, annual N inputs were typically measured in tens of kg/ha With corn & grain crops, annual N inputs are the order of several hundred kg/ha Usually <50% of the N applied as fertilizer is used by the plants Significant amounts of N are left behind in the soils, and can be leached to groundwater by infiltrating water (i.e. precipitation or irrigation) (2) Animal manure (4) Effluent from wastewater treatment plants Sources: Nogales International Wastewater Treatment Plant releases effluent into the Santa Cruz River at a rate of 12,000 to 15,000 acre-feet/yr Dairy & poultry operations Homestead farms – concentrated farms Effluent discharge maintains perennial flow in the river for ~20 miles In General: Farmers have most control over fertilizer N and animal wastes, so control of groundwater nitrates can be achieved most easily through … Significant portion of the discharge infiltrates into the aquifer beneath the wash Best Management Practices for agriculture to hopefully reduce the amount of nitrogen getting into groundwater over time; outreach and education through Groundwater Management Areas and other programs Old WTP = major source of nitrate contamination, E Coli and volatile organic compounds In Iowa, farmers have decreased N-fertilizer use by 18% over 4 years, and still are able to grow as much corn as other Corn Belt farming states. New WTP opened in 2009 substantially reduce ammonia (nitrate) in effluent discharge Better technology at municipal wastewater treatment plants to reduce nitrate levels in effluent discharge What will the impacts be on riparian communities along the wash and River? J. McIntosh UA-HWR (2012) (5) Atmospheric sources of nitrate Nutrients Most atmospheric N comes from combustion; Values highest downwind of power plants or industrial areas Essential elements (C,N,P) needed for growth; but can be a contaminant in high concentrations (e.g. eutrophication of surface waters) Sources and transport of nitrogen deposition in sky islands QuickTime™ and a decompressor are needed to see this picture. High N (nitrite) levels observed in mountain streams during summertime, likely from atmospheric deposition. 3) NOx and particulates transported during dry season QuickTime™ and a decompressor are needed to see this picture. QuickTime™ and a decompressor are needed to see this picture. QuickTime™ and a decompressor are needed to see this picture. are deposited as dry deposition at high elevation. 4) QuickTime™ and a decompressor are needed to see this picture. also contain Raindrops can N and organic carbon species from uptake of soluble gases and aerosol particles. 2) NOxrises and is transported to high in the atmosphere. 1) NOx emissions from Tucson urban core during summer monsoon. N‐containing species (e.g. nitrate and nitrite) are also associated with dust particles that are lifted with wind. Gulf: “Dead” Zone Figure 11: Schematic diagram showing sources of nitrogen deposition and transport in sky-island ecosystems. J. McIntosh UA-HWR (2012) J. McIntosh UA-HWR (2012) Pesticides & Bacteria Vigil (2003) Clean Water What are Pesticides? Pesticides are chemicals that are used to control weeds, insects and other pests Herbicides (weeds) Insecticides (insects) Fungicides (fungi) Nematocides (nematodes = roundworms) Rodenticides (vertebrate poisons) Bioaccumulation of pesticides with increasing trophic level Environmental effects of pesticide use Water quality (more of an issue for aquatic species and predators than humans) A decadal assessment by the National Water-Quality Assessment (NAWQA) Program of the United States Geological Survey (USGS) provides the most comprehensive national-scale analysis to date of pesticide occurrence and concentrations in streams and ground water, based on results from studies completed during 1992–2001. Among the major findings are that pesticides are frequently present in streams and ground water, are seldom at concentrations likely to affect humans, but occur in many streams at concentrations that may have effects on aquatic life or fish-eating wildlife. USGS NAWQA program Toxics Microorganisms Substances that can cause death and deformation of organisms in water Examples include: Dioxins, TCE, petroleum products, pesticides & herbicides 1 gallon of river water may contain more than 1 million bacteria and >10,000 algae. Bacteria in water can cause dysentery, cholera, typhoid, etc. Viruses in water can cause small pox, influenza, yellow fever, etc. Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) Total Coliform Bacteria Group of closely related bacteria that are (with few exceptions) not harmful to humans J. McIntosh UA-HWR (2012) Vigil (2003) Clean Water E. Coli contamination - vectors (1) Food These bacteria naturally live in soil and waters (lake and streams), and in the gastrointestinal tracts of animals Raw meat: E. Coli can get into meat during processing; bacteria can survive if meat isn’t cooked to 160oF; most common food source of contamination E. coli is a type of fecal coliform bacteria commonly found in animal and human intestines; gets into the environment via human and animal waste; these waste products maybe washed into rivers and/or infiltrate into groundwater with precipitation, ending up in drinking water supplies Raw milk or dairy products: bacteria can spread from cow’s udders to milk; make sure products have been pasteurized (heated up to kill bacteria) Raw fruits and vegetables (e.g. lettuce, unpasteurized juice) (2) Water Human or animal feces may get into lakes, pools, and water supplies. People can become infected when city water supplies haven’t been decontaminated with chlorine properly, or when accidentally drinking contaminated pool water, etc. (3) Person to person Not washing hands properly. Symptoms: bloody diarrhea; stomach cramps, nausea & vomiting CDC Transport pathways of pathogens in urban environments Organic substances What are organic compounds? Organic compounds contain CARBON and include: human wastes, animal wastes, food processing wastes, and hydrocarbon (petroleum)-derived substances Biodegradation of organic substances in water removes oxygen - decreasing water quality Stormwater is a major contributor to pathogen transport Some urban areas have combined sewer systems (waste and stormwater are carried in the same pipe system During heavy rain events, runoff can exceed pipe capacity resulting in overflow of raw or partially treated sewage that is dumped into nearby waterways How do we quickly measure organics in water? Biological oxygen demand (BOD) - seeing how quickly oxygen is removed in a water sample gives you an idea of how much organic matter was present. Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) Inorganic substances - Hardness Inorganic Substances - Copper Rocks and minerals; metals; and solids; nitrogen and phosphorus (1) Hard Water: high concentrations of calcium and magnesium scale, low suds Classification Soft Slightly hard Moderately hard Hard Very hard mg/L 0-17 17-60 60-120 120-180 >180 Sources: • Abandoned Mines • Mine leeching ops • Unanticipated releases from tailings or retention ponds • Windborne deposition Cases: • Pinal Ck near Globe EPA Secondary MCL: 1.0 mg/L; metallic taste; blue-green staining; Wildlifel impact: algae, juvenile fish, grazing sheep? Vigil (2003) Clean Water J. McIntosh UA-HWR (2012) Inorganic Substances - Selenium Sources: • Upper Cretaceous/Tertiary Marine Sediments Concentrated by: • Off-channel wetlands • Irrigation return flows • Bioaccumulates Cases: • Lower Colorado Wetlands EPA MCL: 0.05 mg/L; Human health risk: Hair or fingernail loss; numbness in fingers or toes; circulatory problems; Wildlife: deformities in bird embryos Seiler et al, U.S. GEOLOGICAL SURVEY CIRCULAR 1180 Inorganic Substances - Arsenic Sources: • Groundwater • Volcanic rocks also used in: 1. Wood preservatives 2. Paints 3. Dyes 4. Semi-conductors 5. Pesticides 6. Smelting operations EPA MCL: 0.010 mg/L; Human health risks: Skin damage or problems with circulatory systems, and may have increased risk of getting cancer Emerging Contaminants What are Emerging Contaminants? Hazardous materials that are characterized by having: A perceived or real threat to human health, public safety or the environment No published health standards or guidelines Insufficient or limited available toxicology information Information is evolving or being reevaluated Significant new source, pathway or detection limit information National Geographic (2011) 2008 Associated Press (AP) Study J. McIntosh - UA-HWR (2012) Pharmaceuticals and Personal Care Products (PCP) P&PCPs include: Prescription and over-the-counter therapeutic drugs Veterinary drugs Fragrances Cosmetics Sun-screen products Diagnostic agents Vitamins Sources of PPCPs: Human activity (excretion, bathing, flushing down toilet, trash) Residues from pharmaceutical manufacturing (well defined & controlled) Illicit drugs Veterinary drug use, especially antibiotics and steroids Agribusiness J. McIntosh - UA-HWR (2012) Specific Pharmaceuticals Detected in Water Sources Birth control pills Anti-depressants Seizure medication Cancer treatments (e.g. chemotherapy drugs) Cholesterol-lowering compounds Pain kills Tranquilizers What happens to drugs when you ingest, flush down the toilet or put into the trash? Some compounds are easily broken down and processed by the human body or degrade quickly in the environment; others do not degrade and become part of sewage. PPCPs may dissolve easily and make their way into soil and aquatic environments via sewage, treated sewage sludge and irrigation with reclaimed water. www.epa.gov/ppcp/basic2.html Farm animals - source of pharmaceuticals to environment Since early 1950s, antimicrobial agents and hormones have been given to livestock to treat infections and improve growth and feeding efficiency. 40% of US-produced antibiotics are fed to livestock. Manure leaches these agents into streams and groundwater. European ban on growth hormones Health effects for humans & wildlife? Some scientists think that pharmaceuticals don’t pose a threat to humans since they are in such low concentrations in water (typically ppt (parts per trillion) levels) Other scientists say long-term and synergistic effects of pharmaceuticals on humans are not known and advise caution. They are concerned that many of these drugs (endocrine disruptors) may interfere with hormone production. One major concern is that disease-causing bacteria in the environment will become immune to treatment (drug-resistant) because of antibiotics in waterways. Scientists agree that aquatic species are most at risk - their birth to death cycle may entirely occur in potentially contaminated waters. 2000: USGS conducts first nationwide assessment of “emerging contaminants” in streams and groundwater Evidence so far: estrogen (female sex hormone) primarily responsible for deforming reproductive system of fish - hermaphroditic fish observed in England and US (carp downstream from treatment plants in Las Vegas and Minneapolis). Arid regions of the West may be especially vulnerable to the effects of drugcontaminated effluent because of streams that rely heavily on effluent for flow, especially during dry months. Plus, effluent is widely used in irrigation and in some locations as recharge to drinking water aquifers. Plus, there are a lot of retired people in AZ! “The results of this study document that detectable quantities of OWCs occur in U.S. streams at the national scale. This implies that many such compounds survive wastewater treatment and biodegradation” J. McIntosh - UA-HWR (2012) AZ Surface Water Quality Standards Surface water quality standards are established to protect “designated uses” of each stream Aquatic and Wildlife 80% * “Previous research has shown that even low‐level exposure (<0.001 íg/L) to select hormones can illicit deleterious effects in aquatic species” Full Body Contact and Partial Body Contact Domestic Water Source Coldwater Warmwater Ephemeral Effluent Dependent Fish Consumption Agriculture Irrigation and Agriculture Livestock Watering * Kolpin, et al, 2002 How AZ Standards are Applied Numeric standards are maximum or minimum concentration of a parameter to protect a specified designated use Designated Use Core Parameters Aquatic & Wildlife D.O.† Stream flow (if a stream) Sample depth (if a lake) pH Total nitrogen‡ Total phosphorus‡ Dissolved cadmium, copper, zinc & hardness Ag Irrigation pH Total boron & manganese pH Total copper & lead Total arsenic cannot exceed 10 µg/L – Domestic Water Source Dissolved oxygen needs to be greater than 7 mg/L – A&W warmwater Narrative standards provide further protection of water quality. Free from pollutants toxic to humans, animals, plants or other organisms Free from pollutants that cause excessive algae or plant growth. Ag Livestock Fish Consumption Total mercury Domestic Water Source Nitrate/nitrite or nitrate pH Fluoride Total arsenic, chromium or chromium VI, and lead Biocriteria standards measure the health of aquatic communities. AZ’s streams are expected to have an Index of Biological Integrity score of 50-52 based on macroinvertebrates. Body Contact E. coli † pH † Not required if ephemeral ‡ If nutrients standard established Source: Sutter, ADEQ Source: Sutter, ADEQ TMDL Program for “Impaired” waters A Total maximum Daily Load (TMDL) analysis is completed to determine Sources of pollutants Load reductions required to meet standards An implementation plan for improving water quality Factors: Load Allocations (LA) Non-point sources (i.e. precipitation runoff) Non-regulated Monitoring in Turkey Creek Waste Load Allocations (WLA) Point source (i.e. end of pipe discharge) Regulated thru AZPDES Margin of safety (MOS) Considers natural background TMDL= ∑LA + ∑WLA + MOS Source: Sutter, ADEQ