Griffy Reservoir Water Sampling Locations

7 Griffy
6
Lake

3
4
5 1

10
2

University
Lake

Sample Locality

Note: Sites 9 and 10 were added in 2011. (Site 3 was dry due to low water level)
Griffy Field Teams and Water Sample IDs
 Data Analysis
and Presentation (2010)
Temp pH SpC Redox DO Alkalinity F- Cl- NO2- Br- NO3- PO43- SO42- Ca2+ Mg2+ Na+ K+

(oC) (µS/cm) (mV) (mg/L) (mg/L) (mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

GRIFFY LAKE –
7 Sept 2010

Boat House Dock B1 23.0 7.94 590 141.1 165.9 0.12 49.4 0.94 1.21 18.18 35.07 12.58 38.25 11.35

Boat House Dock #2 0.12 22.7 1.48 1.72 1.80 11.04 41.14 11.90 34.75 11.48

inlet sample 1 - JB 22.0 8.10 556 4.4 159.3 0.28 46.5 0.91 1.16 18.37 58.02 20.52 24.30 2.07

Inlet sample 1 group A 0.10 54.4 0.03 0.04 16.55 50.50 9.03 13.60 1.88

Inlet Group A 0.01 75.0 0.15 13.28 14.39 5.39 17.65 1.45

"Pond" group A 30.4 7.89 215 16.9 54.2 91.8 0.02 0.13 0.10 10.24 14.62 5.39 16.50 1.91

Causeway Group 2 B 25.0 6.71 637 120.0 8.5 148.6 0.04 63.2 0.24 0.33 0.51 32.27 36.42 9.02 26.60 4.50

Causeway 2 25.0 6.96 530 155.6 0.09 55.1 0.17 0.23 0.30 30.94 42.85 10.24 30.50 5.99
 The Milliequivalent (meq/l),
Units of Equivalent Weight
An equivalent is the amount of an anion or cation species needed
to add or remove one mole of electrons from a system.

A milliequivalent is defined as 1/1000 of an

equivalent of a chemical element, radical or
compound. Its abbreviation is "mEq" or "meq".

Concentration in mg/L * valence

Concentration in meq/l = -----------------------------------------------
F.W. of the ion

•Milliequivalents can be expressed in milligram units (mg). To

convert grams to milligrams, multiply the value by 1,000.

•Milliequivalents can be calculated using millimoles (mmol). The

equation to calculate mEq from mmol is mEq = mmol x V. In this
case, the unit of measurement is millimole (mmol), not grams.
Converting Ionic Concentrations to
Units of Equivalent Weight (meq/l)
Concentration in mg/L * valence
Concentration in meq/l = -----------------------------------------------
F.W. of the ion

Conc. Conc.
Ion Valence F.W.
(mg/l) (meq/l)
Ca+2 151 +2 40.08 7.53
Mg+2 23 +2 24.31 1.90
Na+1 165 +1 22.99 7.18
K+1 19 +1 39.10 0.49
Total meq/l cations: 17.10
HCO3-1 401 -1 61.02 6.57
SO4-2 58 -2 96.06 1.21
Cl-1 345 -1 35.45 9.73
Total meq/l anions: 17.51
 EMP balances:
Total meq/l cations: 17.10 meq/l difference = 2.39%

Total meq/l anions: 17.51 meq/l difference = 2.42%

Difference: 0.41 meq/l

•An acceptable analyses will have a %-difference that is less than 10%
Though, less than 5% is best.
Indicates you have accounted for all the major ions in the system and
have a “complete” analysis.
If balance is off, not accounting for an ion such as Fe, Si, Al, or OH,
incorrect dilutions,
very dilute samples,
math errors,
contamination
 Stiff Diagram
Stiff diagrams are graphical representation of
water chemical analyses, first developed by H.A. Stiff Diagram –sample 3A
Stiff in 1951.
Mg SO4
A polygonal shape is created from three or four
parallel horizontal axes extending on either side of Ca HCO3
a vertical zero axis. Cations are plotted in
milliequivalents per liter on the left side of the Na Cl
zero axis, one to each horizontal axis, and anions
are plotted on the right side. Stiff patterns are
0
useful in making a rapid visual comparison
between water from different sources.
Other possible pairs:
ADVANTAGES
Fe NO3
• Can help visualize ionically related waters from
which a flow path can be determined, or;
K NO3
• If the flow path is known, to show how the
ionic composition of a water body changes
Fe CO3
over space and/or time.
DISADVANTAGE
• Only one analysis per plot.
Application of Stiff Diagrams
A.
Figure 7. Stiff diagrams for samples from the
Queen City and Sparta Aquifer Systems
Abbott, M., 2008, Final Report: Evaluation Groundwater
Chemistry in Gonzales County, Texas and Technical and
Educational Assistance to Groundwater Conservation
Districts in Texas: US EPA .
B.
Figure 5. Stiff diagrams annotated on an engineering
plan map of Horsetooth Dam that show different
chemistry (polygon shapes) for each piezometer
located in the embankment and alluvium.
Craft, D., 1999, Summary and Interpretation of Chemistry
Data for Reservoir, Seeps, and Groundwater from
Horsetooth Dam, Colorado-Big Thompson Project, Ft.
Collins, Colorado, Technical Memorandum D-8290/99-
001, U.S. Bureau of Reclamation, Dam Safety Office,
Denver, Colorado.
Abbott, M., 2008, Final Report: Evaluation Groundwater
Chemistry in Gonzales County, Texas. EPA Report
 Horsetooth Dam, Colorado-Big Thompson Project, Ft. Collins, Colorado

Craft, 1999.
 Piper Diagram
A piper diagram is a graphical
representation of the chemistry of a
water sample or samples.
The cations and anions are shown by
separate ternary plots.

The apexes of the cation plot are

calcium, magnesium and sodium
plus potassium cations. The apexes
of the anion plot are sulfate,
chloride and carbonate plus
bicarbonate anions.

The two ternary plots are then

projected up onto a diamond. The
diamond is a matrix transformation
of a graph of the anions and cations.

In Piper diagrams the concentrations Figure 1-7 from Kehew (2001). Classification of
are expressed as %meq/L. hydrochemical facies using the Piper plot.
 % meq/l

Conc. Conc.
Ion
(mg/l)
Valence F.W.
(meq/l) (% meq/l)
Ca+2 151 +2 40.08 7.53 44.34
Mg+2 23 +2 24.31 1.90 11.21
Na+1 165 +1 22.99 7.18 41.99
K+1 19 +1 39.10 0.49 2.46
Total meq/l cations: 17.10 100
HCO3-1 401 -1 61.02 6.57 37.52
SO4-2 58 -2 96.06 1.21 6.91
Cl-1 345 -1 35.45 9.73 55.57
Total meq/l anions: 17.51 100
 Cations
Conc. Conc.
Ion
(mg/l)
Valence F.W.
(meq/l) (% meq/l)
Ca+2 151 +2 40.08 7.53 44.34
Mg+2 23 +2 24.31 1.90 11.21
Na+1 165 +1 22.99 7.18 41.99
K+1 19 +1 39.10 0.49 2.46
 Anions
Conc. Conc.
Ion
(mg/l)
Valence F.W.
(meq/l) (% meq/l)
HCO3-1 401 -1 61.02 6.57 37.52
SO4-2 58 -2 96.06 1.21 6.91
Cl-1 345 -1 35.45 9.73 55.57
Projection
into the
upper
diamond-
shaped field
 ADVANTAGES
• Many water analyses can be
plotted on the same diagram.
• Can be used to classify waters
by hydrochemical facies.
• Can be used to identify mixing
of waters.
• Can track changes through
space and temporal
relationships.

DISADVANTAGES
• Concentrations are
renormalized.
• Cannot easily accommodate
waters where other cations or
anions may be significant.

Figure 1-7 from Kehew (2001). Classification of

hydrochemical facies using the Piper plot.
 Application of
A.
Piper Diagrams
B.

Figure 2: Piper plot of historical background

Figure 3: Piper diagram (Piper, 1944) showing regional
(letters) and site (numbers) water quality
mixing trends. Fields show localized well-defined
analysis.
regional and subregional mixing trends. Important end-
.McLin, SG, 1986, Evaluation of Aquifer
member compositions and high-volume springs of the
Colorado Plateau region. Contamination from Salt Water Disposal Wells:
Proceedings of the Oklahoma Academy of
Crossey, LJ, Karlstrom, KE, Springer, AE, Newell, D, Hilton, DR,
Science, 66: 53-61.
Fischer, T, 2009, Degassing of mantle-derived CO2 and He from
springs in the southern Colorado Plateau region—Neotectonic
connections and implications for groundwater systems
Geological Society of America Bulletin, 121:1034-1053.
 Durov Diagram
• Primary: Cations (i.e. Na + K, Ca and Mg) and Anions (i.e. Cl,
HCO3 and SO4), and total cations vs. total anions only.
Data points
• Expanded: TDS and pH added

TDS (mg/L)
Anions
(norm)

Cations Total Cations

(norm)
vs.
Total Anions

pH Source: RockWare Inc.,

http://www.rockware.com/product/gallery.php?id=150
 Durov Diagram
Description/ Type of data : a composite plot consisting of 2 ternary diagrams where the
cations of interest are plotted against the anions of interest (data is normalized to 100%);
sides form a binary plot of total cation vs. total anion concentrations (this plot can be
contoured); expanded version includes TDS (mg/L) and pH data added to the sides of the
binary plot to allow further comparisons.
Use: to graphically illustrate cation/anion concentrations, relative to TDS and pH.
– For example, using Griffy Lake samples IC and AAS data, we can plot the ion
concentrations, then calculate the TDS from our specific conductivity field
measurements, and use the pH field measurements. Because we sampled at several
locations (i.e. causeway, pond, etc.), we can use those as data groups to see if there are
any spatial variations in water chemistry , and if so, could they be related to a different
TDS content, different pH, or both.
Example case studies:
– Vermeulen, P., and Usher, B., 2009, The effect of graben structures on the migration of
groundwater contaminants at an industrial site: Environmental Geology, 58:739-749.
• Different water chemistry in aquifers on the opposite sides of graben structures
– Petalas, C.P., and Diamantis, I.B., 1999, Origin and distribution of saline groundwaters in
the upper Miocene aquifer system, coastal Rhodope area, northeastern Greece:
Hydrogeology Journal, 7:305-316.
• Variations in ionic compositions of saline vs. fresh water
 The intersection of lines
extended from the two sample
points on the triangle to the
central rectangle gives a point
that represents the major-ion
compositions on a percentage
Durov Diagrams
basis. From this point, lines
extending to the adjacent scaled
rectangles provide for
representations of the analyses
in terms of two parameters
selected from various
possibilities, such as total major-
ion concentrations, total
dissolved solids, ionic strength,
specific conductance, hardness,
total dissolved inorganic carbon,
or pH.

Durov SA, 1948, Natural waters and graphic representation of

their compositions. Dokl Akad Nauk SSSR 59:87–90.
 Expanded Durov Diagram

cations

anions

D. K. Chadha, 1999, A proposed new diagram for geochemical classification of natural

waters and interpretation of chemical data: Hydrogeology Journal 7:431–439.
 Schoeller Diagram
A Schoeller Diagram is a semi-logarithmic diagram of the concentrations of
the main ionic constituents in water (SO4, HCO3, Cl, Mg, Ca, Na/K) in
equivalents per million per kg of solution (mEq/kg).
• An equivalent is the amount of an anion or cation species needed to add or remove one
mole of electrons from a system.
• Concentrations of each ion in each sample are represented by points on six equally
spaced lines and points are connected by a line.
• The diagram gives absolute concentration, but the line also gives the ratio between
two ions in the same sample
• If a line joining two points representing ionic concentrations in a single sample is parallel
to another line joining a second set of concentrations from another sample, the ratio of
those ions in those samples are equal.

Converting data in mg/L to milliequivalents:

• Multiply mg/L by one over the milliequivalent weight
(which can be looked up in tables).
• This gives mEq/L, using mg/kg will yield mEq/kg

• Milliequivalent weight= (atomic weight)/(valence state

x 1000)
 Schoeller Diagram
Studies that utilize Schoeller diagrams :
• Chemical quality of waters
• Groundwater/Surface water studies, hydrology in general
• Waste Water potentially from any Economic Geology related Industry (oil, mining,
etc) or runoff from agriculture
• Mineral exploration

• Barbiéro, L., et al. Geochemistry of water and ground water in the

Nhecolândia, Pantanal of Mato Grosso, Brazil: variability and
associated processes. Wetlands, v. 22, no. 3 (2002), pp. 528-540.
• Investigated possibility that saline and freshwater lakes in Pantanal remain
connected by a sub-surface aquifer.
• Van Voast, Wayne A. Geochemical signature of formation waters
associated with coalbed methane. American Association of
Petroleum Geologists (AAPG) Bulletin, v. 87, no. 4 (April 2003), pp.
667–676.
• Described typical chemistry of water associated with coalbed methane that can
be an exploration tool, regardless of formation lithology or age.
• Hill, C. Geology of Carlsbad Cavern and other caves in the Guadalupe
Mountains, New Mexico, and Texas. New Mexico Bureau of Mines &
Mineral Resources Bulletin 117 (1987). Figure 5 (Barbiero et al 2002). Schoeller diagram of three
• Huizar A., et al. (1998) 'Patterns of groundwater hydrochemistry in representative fresh (a) and concentrated (b) waters. 1:
Corixo; 2: Negro River; 3: Lagoa; 4 and 5: Water table in
Apan-Tochac sub-basin, Mexico / Hydrochimie des eaux souterraines cordilheira; 6: Salina.
du sous-bassin Apan-Tochac, Mexique'. Hydrological Sciences Journal,
43: 5, 669 - 685.
 Schoeller Diagram

[semi-logarithmic axis]

cations anions
 Radial Plot
What is a radial plot? What type of data is used?
• A radial plot is a diagram • In this plot, the data shows
used to compare samples or milliequivalents/kilogram
values against each other, (meq/l) for various ions and
according to a standard compounds.
measurement.
• The circular plot type allows
you to easily see how values
compare based on the
shape of each section of
plot.
 Radial Plot
What kinds of studies? Examples
• Studies that involve direct • Mixing phase of sea water and fresh
water
comparisons:
– Ionic concentrations
– Wind speed and velocity
– Seasonal plant productivity
– Fission track dating
– Mineral availability

• Wind direction and frequency

Example citations:
• Escolero. et all. Geochemistry of the Hydrogeological
Reserve of Meridia, Yucatan, Mexico. Universidad
Nacional Autonoma de Mexico. 2005.

• Garcia et all. Effects of Wind on Background Particle

Concentrations at Truck Freight Terminals. J Occup
Environ Hyg. 2007.
 Time Series - pH
Plot description
This plot describes the relationship between pH values and dates between Aug 3rd and
Aug 25th in 2003. The pH values were kind of scattered, ranging from 6.75 to 7.05, with
an average of 6.9. The pH kept increasing for the first six days and arrived at the highest
value (7.05) on Aug 7th and Aug 8th, followed by a continuous decrease until Aug 11th.
On Aug 13th, the pH values rose again and stayed at 6.95 for the following 7 days. The
pH then declined and went through several fluctuations and reached the lowest value on
Aug 24th.

Type of data
The data used in the plot was the directly measured pH without any transformation.
Many other characteristic parameters, such as temperature, conductivity, alkalinity and
so on, can also be plot as functions of time series. This plot is probably the
environmental monitoring result of the pH variation in a river, a lake or a wastewater
discharge outlet.
 Time Series - pH
•Types of studies in which pH, or other similar data, is examined over time
•Evaluating ocean acidification
•Effects of rising sea surface temperature on pH through time
•Carbonate concentrations
•Monitoring seasonal cycles that affect pH, pCO2, and salinity
•Buffering capacity of a system through time

•Also used frequently in fields outside of water chemistry

•Economics (ie the stock market)
•Quantum physics
•Mortality rates
•Population studies
Specific Studies
• R. A. Quick and A. E. Ogden, Hydrochemistry as a means of
Delineating Groundwater flow patterns in the Edward’s Aquifer,
Time Series
San Marcos, Texas, U.S.A.
•Researchers plotted pH, temperature, dissolved
oxygen, discharge, sulfate, and conductance, over
the twelve month duration of their study to
determine the parameters of a series of aquifer
springs. The study was aimed at investigating the
validity of a model that suggested the spring would
cease to flow in 2020. In this process, researchers
discovered that there are actually two chemically
unique groups of springs and that discharge had a
more profound role in altering water chemistry for
one group as opposed to the other.
•Bredemeier, Dohrenbusch, and Murach, Response of soil water
chemistry and fine-roots to clean rain in a spruce forest ecosystem
at Solling, FRG
•In the Solling experimental forest in central
Germany a clean rain roof experiment is conducted
in a 60 year old Norway Spruce (Picea abies KARST.)
stand. In this experiment with application of
artificially prepared pre-industrial throughfall there
is now a time series of soil water chemistry data
from about 2 yr of pre-experiment and 3.5 yr of
manipulation treatment.
 Time Series
Variable

Time
[ Julian days, calendar dates, hours, minutes, seconds, years, decades, etc.]
 Box and Whisker plot

• Box and Whisker is a summary plot of 5 statistics: minimum, maximum,

median and the lower and upper quartiles. Mean is sometimes shown as well.

• Multiples plots can be connected to show the variance of data over time or
compared to other sites to show differences.
 Box and Whisker Plot
• It is often used in Environmental Chemistry to show
water quality variance over time, between areas, and
in concentration studies.
– Allows comparison range, median, spread, etc more
conclusion can be drawn than from a time plot
• Examples
– Knudson, A.C., M.E. Gunter, 2002, Sedimentary Phosphorites—An
Example: Phosphoria Formation, Southeastern Idaho, U.S.A.: Reviews in
Mineralogy and Geochemistry, v. 48, no. 1, p. 363-389.

– Lmeida, C.A., et al., 2010, Mineral Paragenesis , Alteration , and

Geochemistry of the Two Types of Gold Ore and the Host Rocks from the
Carlin-Type Deposits in the Southern Part of the Goldstrike Property ,
Northern Nevada: Implications for Sources of Ore-Forming Elements , Ore
Geologic Society, v. 105, no. 1, p. 971-1004.
 Box and Whisker Plot
combined in a Time Series Plot