Download What`s in the Water? Outline – Major WQ Indicators Bottom line: one

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
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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
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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