Trace and minor metals analysis of four streams in central Texas

Jessica Garcia
Nick Kelley
Nathan Roddy
Matt Webb








Geochemistry of Natural Waters
Dr. Franco Marcantonio
December 03, 2012
Metals analysis of four Texas streams 2


Procedure
Water samples were collected directly from the streams using sterile polypropylene
centrifuge tubes. Teams 2-4s samples were put on ice after being collected and then frozen for
approximately two days. The samples were then allowed to thaw at room temperature before
being filtered and acidified. This most likely affected the results due to the samples being
exposed to freeze-thaw activities and acidified much later than recommended affecting the
chemistry. The samples were filtered using a vacuum filtration system. Team 1s samples were
run through a 0.4 micron polymer filter and Teams 2-4s samples were run through 1 micron
cellulose filters. All of the samples were then acidified with a 2% HNO3 solution. HNO3 was
used to decompose ion pairs and prevent post-precipitation of magnesium and calcium salts, as
well as prevent the growth of molds and algae. Four to five dilution standards were prepared
from a known stock solution which included all of the elements of interest in known ratios. For
an internal standard, Indium-115 was added at a concentration of 10 ppb to the water samples
and dilution standards. The dilution standards are bracket concentrations of all the elements in
the sample and the dilution percentage is changed by roughly an order of magnitude for each
dilution. The indium corrects for temporal variability, resulting in a more precise working curve.
A working curve is a plot of the analytical signal (the instrument or detector response) as a
function of analyte concentration. These working curves are obtained by measuring the signal
from the series of standards of known concentration. The working curves are then used to
determine the concentration of an unknown sample, or to calibrate the linearity of an analytical
instrument. If all the working curves are precise and straight with very high R^2 values, the
samples can then be analyzed. The resulting counts can then be converted to concentrations
using the working curves.

Metals analysis of four Texas streams 3


Hydrological Considerations
We decided to consider the hydrological aspects of the four streams included in this
analysis. These four stream bodies can generally be classified in three categories based on size.
The Brazos River is a large statewide river; at 840 miles long it is the longest river contained
wholly within the state. It has numerous large reservoirs along its length and is used extensively
for water supply, hydropower, and irrigation. The Navasota River is a regional river of 125
miles, much shorter than the Brazos, it is moderately dammed. The result is that flow regimes in
these two systems are a function of precipitation (event flows), groundwater interaction (base
flows), and reservoir releases. Flow rates for these two systems are also gaged by USGS making
water chemistry vs. flow rate comparisons possible. By comparison, Lick Creek and White
Creek are much smaller systems and are likely to be dominated by local precipitation events.
For this portion of our analysis, we used Alexs data. This was due to the fact that we were
considering the impact of flow and precipitation events and were too tightly bunched temporally
in the group versus group data. Alexs data can generally be categorized as being taken from the
February and August timeframes. Source data originated from the National Weather Service
(precipitation) and from USGS (flows) and are shown in Figure 1 and Table 1 below.

Metals analysis of four Texas streams 4



Figure 1: Study Area Temperature and Precipitation
Source: National Weather Service

The relationship being studied was the effect of precipitation, evaporation, and flow rate
on chemical concentration. Bicarbonate was chosen as the element of study due to its high
concentration and high variability. Inspection of all data in Alexs data set reveals that almost all
cations and anions follow the behaviors noted in the bicarbonate study.
Our theory was that water systems would become more highly concentrated with
dissolved solids during times of reduced rainfall. The potential for this effect was first analyzed
on Lick and White Creeks. Quite fortunately, the precipitation and evaporation regimes were
very different across the two sampling timeframes. Evaporation is a strong function of
temperature and the approximated mean during the first sampling at each site as taken visually
from Figure 1 was 60 F while the second sampling was about 20 degrees higher with afternoon
Metals analysis of four Texas streams 5


highs around 100 F. The precipitation amounts (Table 1 below) were much higher during the
first sampling versus the second, 12 inches to 4 inches respectively. The lower precipitation and
higher evaporation (as proxied by temperature) should lead to high dissolved concentrations of
bicarbonate. Thats exactly what was found, concentrations were three times the concentration
of the first samplings.
The Navasota and Brazos Rivers have the extra complication of receiving discharge from
upstream reservoirs (Limestone and Whitney, respectively). The first sampling of the Navasota
had high precipitation and high discharge. One would expect the river to have concentrations
slightly lower than Limestone due to dilution and that is exactly what the data indicates: 89 ppm
at Limestone and 83 ppm in the Navasota. During the second sampling with low flows and low
precipitation, significant increases in concentration might be expected and that is what the data
indicates as well, with concentrations increasing to 378 ppm.
We felt very good until we looked at the Brazos. It showed a very consistent bicarbonate
concentration moderately higher than Lake Whitney despite large changes in precipitation,
evaporation, and flow rate. This behavior indicates the complicated nature of natural processes
and would require further study. As such, we lack an explanation for this behavior. It should be
noted that had we substituted Na for bicarbonate as our representative compound, this confused
behavior would not have been exhibited. We decided on bicarbonate specifically because it
showed that small studies often result in insufficient conclusions.

Metals analysis of four Texas streams 6


Source Sample Date
(2012)
Preceding
Precip
(Monthly inches)
Discharge
(cfs)
Concentration
HCO3
(ppm)
Lick
2/14 12 NA 128
7/23 4 408
White
2/18 12 NA 122
7/26 4 376
Navasota
2/20 12 1100 83
9/10 3 8 378
Brazos
3/21 6 2500 211
8/16 0 500 203
Limestone 8/3 NA NA 89
Whitney 8/3 NA NA ~180
Table 1: Concentration Comparison

Mineral SI
In order to see what minerals would precipitate from the various concentrations of all the
ions from the samples that we collected as well as those provided from Alexs personal
collection, we used Visual MINTEQ to see which combinations of ions would produce minerals.
The program takes into account the temperature, pH, alkalinity, and concentration of each
dissolved ion in the water sample and produces an extensive table describing the molality and
activity of every conceivable ion as well as certain molecules. The main purpose of using the
MINTEQ program is to identify what minerals are present and to see how saturated the water is
relative to each mineral.
Metals analysis of four Texas streams 7


Visual MINTEQ provided a very extensive list of possible mineral combinations from the
inputted data derived from the ICPMS. Many of the species it provided are very abstract and
uncommon, whether it is from the scarcity of the element or the state that the ion has to be in
order for a mineral to precipitate. The vast majority of the ions tested showed most
combinations of minerals from the dissolved ions had a slightly negative SI number on the order
of -0.1 to relatively high negative SI numbers around -70 for a particular lead carbonate hydroxyl
mineral. Most SI numbers however were much less extreme and were on the range of around -1
to -20. For example, Table 2 shows all four streams are under-saturated with the common
evaporite mineral gypsum, and calcite/aragonite is also slightly under-saturated.
There were of course some mineral combinations that were supersaturated. Many of the
supersaturated minerals are the ones that are much more common and less obscure than many of
the under-saturated minerals. The range of SI numbers for the supersaturated minerals is
actually larger than the range that corresponds to the under-saturated minerals. This is not
because of extremely supersaturated minerals that might precipitate out of the water; it is because
many minerals are so close to equilibrium that their SI numbers are quite low. An example of a
low saturation index number is demonstrated in Table 2, Team 1s Brazos data showed that
gibbsite has a SI of 0.03 meaning that it is closer to being in equilibrium and most any other
mineral. In fact, gibbsite is so close to being in equilibrium when Team 1 collected their sample,
that when the remainder of the teams collected samples gibbsite was under-saturated. Low
positive SI numbers are expected to be lower and closer to equilibrium than minerals that are
under-saturated. This is only true when the sampling site is not close to a major point source area
of erosion or tributary nearby that would add excess amounts of dissolved ions to the water.

Metals analysis of four Texas streams 8


Saturation
Indices
Hematite
(Fe2O3)
Cupric Ferrite
(CuFe2O4)
Calcite
(CaCO3)
Gibbsite
(AlOH3)
Gypsum
(CaSO42)
Team1
Brazos 13.01 11.70 0.60 0.03 -1.64
Navasota 14.91 13.14 -0.52 0.73 -2.37
White 9.42 14.67 0.31 0.49 -1.37
Lick 15.26 13.46 -0.17 2.18 -2.19
Team 2
Brazos 13.96 13.23 1.07 -0.29 -1.22
Navasota 15.93 14.98 0.39 0.73 -2.40
White 15.73 15.50 1.00 0.49 -1.38
Lick 15.99 15.01 0.24 1.16 -2.02
Table 2: Common Mineral SI Indices from Visual MINTEQ

The minerals in Table 2 were chosen due to their abundance, familiarity, and ability to
track the effects of precipitation events upstream. Each mineral is composed of important ion,
both cation and anions, found in natural waters. Iron is an important minor ion to test for in
natural waters because iron is a good indicator of pollution rates from acid mine drainage and
certain ecosystems, and of course erosion from other iron bearing minerals such as magnetite and
pyrite and any mafic rocks that is a drainage basin. In our case, there are not any mafic rocks
present on the surface or large mining operations upstream, thus shrinking the sources that could
introduce iron into the streams affecting the SI values. Generally speaking, hematite and cupric
ferrite to an extent are usually found in most natural waters, and in this particular case, they are
Metals analysis of four Texas streams 9


both clearly fully supersaturated and consistent probably resulting from oxide minerals in the soil
or industrial pollution.
As mentioned earlier, the Brazos has the furthest reach and the highest flow rate and
discharge of the four streams that were tested, with the headwaters originating to the northwest
portion of Texas where evaporite deposits such as gypsum and clay soils are very prevalent.
With that said, the Brazos is exposed to a greater variety of rock types over it course and is likely
to have a greater variety of minerals and dissolved ions as well. It is also true that, due to its
size, the concentrations of ions are not likely to change as much as either White or Lick would
between and after precipitation events. For example, the result of a large precipitation event that
occurs around the headwaters, where large amounts of gypsum/anhydrite and fine gain clay soils
are eroded, would not readily be noticed at our testing site in College Station due to the dilution
effects of tributaries and springs adding their own blend of ions as well as other precipitation
events causing more runoff and erosion. As a result, the high quantity of gypsum that is
inevitably eroded to the northwest is diluted to the point the point of having similar SI values as
all the other streams. The Navasota River is about an eighth as along as the Brazos, and White
and Lick are relatively very small and only have local reaches equates that the SI values for the
mineral will have a greater percentage of change after a precipitation event and during periods of
drought. The SI values are dictated directly by the local strata a rather than by the geology
hundreds of miles away.
While these differences and similarities discussed are some of the more important and
recognizable minerals, they were not the only connections that could be made. There were many
other examples of less common minerals that would require much more research than the scope
of this paper allows.
Metals analysis of four Texas streams 10


Quality
Contaminates and trace elements find their way into water sources both naturally and
through human activities. At certain amounts these elements can become harmful when
consumed by humans and as a preventative measure the Environmental Protection Agency
(EPA) and the World Health Organization (WHO) have created guidelines and regulations for
drinking water quality. In the United States the EPA has created National Primary Drinking
Water Regulations. These regulations are legally enforceable standards that apply to public water
systems. Primary standards protect the health of the public by limiting the levels of contaminants
in drinking water. There is a set Maximum Contaminant Level (MCL) which is the highest level
of a contaminant that is allowed in drinking water. Globally, WHO has created a set of
provisional guideline values for safe drinking-water at which there are no significant risk to
health over a lifetime of consumption.
The data collected, specifically for Team 1 and Teams 2-4 (avg.) were compared to the
MCLs designated by the EPA and the guidelines created by the WHO. The elements examined
were primarily trace metals, including Mg, Al, Ba, Fe, Mn, Cu, Cd, Pb, and U. Neither the EPA
nor WHO designated a value for magnesium because of the uncertainties surrounding mineral
nutrition from drinking-water. There is insufficient scientific information on the benefits or
hazards of long-term consumption of very low mineral waters to allow any recommendations to
be made. The WHO also did not set a guideline for aluminum based on the fact that a health-
based value of 0.9 mg/l could be derived from the Joint FAO/WHO Expert Committee on Food
Additives provisional tolerable weekly intake (PTWI), but this value exceeds practicable levels
based on optimization of the coagulation process in drinking-water plants using aluminium-
based coagulants: 0.1 mg/l or less in large water treatment facilities and 0.2 mg/l or less in small
Metals analysis of four Texas streams 11


facilities. Also guideline values for iron and manganese were not established due to levels of
manganese and iron not bringing health concern at levels found in drinking-water. Natural fresh
waters contain iron at levels ranging from 0.5 to 50 mg/l. At levels above 0.3 mg/l, iron stains
laundry and plumbing xtures. There is usually no noticeable taste at concentrations below 0.3
mg/l, although turbidity and color may develop at concentrations higher than 0.1 mg/l,
manganese causes an undesirable taste in beverages and stains sanitary ware and laundry but
does not pose a health concern at the levels found in drinking water. Both the EPA and WHO
have designated guideline and MCL values for barium, copper, cadmium, lead, and uranium
noted in Tables 3 and 4.

Table 3: Team 1s ICPMS results compared to WHP and EPA drinking water MCLs

Mg Al Ba Fe Mn Cu Cd Pb U
I
C
P
M
S

R
e
s
u
l
t
s

(
p
p
b
)
Brazos 5662.79 1.58 62.89 0.87 0.64 0.83 0.05 0.05 0.68
Navasota 1489.70 18.90 20.90 30.43 2.36 3.94 0.16 0.28 0.18
White 1548.29 10.89 24.40 25.24 3.94 6.51 0.08 0.24 0.99
Lick 1786.60 26.18 23.66 40.06 3.97 3.87 0.12 0.34 0.25
WHO (ppb) -- -- 700 -- -- 2000 3 10 30
EPA (ppb) -- 50-200 2000 300 50 1300 5 15 30
Metals analysis of four Texas streams 12



Table 4: Teams 2-4s (avg.) ICPMS results compared to WHO and EPA drinking water MCLs

When Team 1s data is compared to the values stated by the WHO and the EPA,
all of the elements concentrations fall into a safe range as observed in Table 3. Magnesium levels
were highest in the Brazos and increasingly less in Lick Creek, White Creek, and Navasota
respectively ranging from 5662.79 ppb to 1489.70 ppb. Team 2-4s (avg.) values of elements are
well within a healthy range when compared to the WHO and EPAs standards as well as seen in
Table 4. The levels of magnesium are highest in the Brazos and increasing less so in White
Creek, Navasota, and Lick Creek, respectively ranging from 6568.13 ppb to 1551.87 ppb. In all
of our data aluminum is highest in Lick Creek perhaps due to the feldspar and clay content in the
area. Barium has the highest concentration in the area of the Brazos River. Major sources of
barium in drinking water come from discharge of drilling wastes, discharge from metal
refineries, and erosion of natural deposits. The highest amount of iron is found in Lick Creek
with a value of 40.06 ppb for Team 1 and 25.91 ppb for Team 2-4 (avg.). This iron concentration
is most likely due to oxide minerals being dissolved into the groundwater. As for cadmium the
Mg Al Ba Fe Mn Cu Cd Pb U
I
C
P
M
S

R
e
s
u
l
t
s

(
p
p
b
)
Brazos 6568.13 3.16 61.06 1.43 0.20 0.76 0.06 0.04 0.62
Navasota 1885.42 12.38 26.36 14.93 0.21 2.24 0.11 0.09 0.27
White 2231.56 12.22 34.86 10.39 0.66 7.47 0.06 0.07 2.46
Lick 1551.87 20.07 21.86 25.91 0.23 3.72 0.19 0.12 0.15
WHO (ppb) -- -- 700 -- -- 2000 3 10 30
EPA (ppb) -- 50-200 2000 300 50 1300 5 15 30
Metals analysis of four Texas streams 13


highest amounts for all groups was detected in White Creek in all likelihood due from erosion of
natural deposits, discharge from metal refineries, or runoff from waste batteries and paints.
Amounts of manganese, cadmium, lead, and uranium ranges are not only much lower than the
MCLs or standards; they are not variable enough for mentioning and seen in Figures 2 and 3.


Figure 2: Team 1 Data excluding Mg


Figure 3: Teams 2-4 averaged data excluding Mg
0
10
20
30
40
50
60
70
Al Ba Fe Mn Cu Cd Pb U
Brazos
Navasota
White
Lick
0
10
20
30
40
50
60
70
Al Ba Fe Mn Cu Cd Pb U
Brazos
Navasota
White
Lick
Metals analysis of four Texas streams 14


Conductivity is a measure of the ability of water to pass an electrical current.
Conductivity in water is affected by the presence of inorganic dissolved solids such as chloride,
nitrate, sulfate, and phosphate anions, and sodium, magnesium, calcium, iron, and aluminum
cations. Organic compounds like oil, phenol, alcohol, and sugar do not conduct electrical current
very well and therefore have a low conductivity when in water. Conductivity is also affected by
temperature: the warmer the water, the higher the conductivity. According to the EPA, the
conductivity of rivers in the United States generally ranges from 50 to 1500 mhos/cm. Studies
of inland fresh waters indicate that streams supporting good mixed fisheries have a range
between 150 and 500 hos/cm. Conductivity outside this range could indicate that the water is
not suitable for certain species of fish or macro-invertebrates. Industrial waters can range as high
as 10,000 mhos/cm. The conductivity levels found in the Brazos area are stated in Table 5 and
fall in the range of normal conductivity for the United States although all of the fluvial bodies
have a conductivity above 500 mhos/cm and may indicate the water is not suitable for certain
aquatic life.

Source
Conductivity
(Team 1)
Conductivity
(Teams 2-4)
Lick 800.00 882.00
White 533.00 782.0
Navasota 615.00 782.00
Brazos 862.00 1027.00

Table 5: Conductivity values

Metals analysis of four Texas streams 15


Conclusion
In this paper, we examined several different aspects regarding the water samples
we collected in order to better understand what process affect the concentration of the dissolved
ions, the saturation of minerals comprised of the dissolved ions, and how the quality of the water
compares to regulated standards. We have shown that our four streams are affected by dams,
precipitation events, and upstream lithology. Chemical concentration behavior was dominated
by precipitation effects, especially in the smaller stream systems of Lick and White Creeks.
Periods of low precipitation and high evaporation led to dramatically higher concentration levels.
This was also generally true of the larger, dammed systems except the chemical concentration
generally mimicked the reservoir upstream of sampling. This was surprisingly not true of
bicarbonate concentration in the Brazos.
The analysis of the results from Visual MINTEQ program gave good insight to
what minerals are likely to form from the waters, which again gives insight to the origins of the
waters as well as how the lithology and soil type changes during the span of the stream by telling
the saturation indexes of many different mineral present. Upstream lithology definitely plays a
factor in all water both surface and ground, but might not be apparent if far enough away from
the source. Such is the case with gypsum, the headwaters of the Brazos originate in the
northwest portion of the state where there are high amounts of evaporite deposits but due to high
solubility and distance, our results showed that the water was under-saturated.
Finally, we discussed both the national and international regulatory standards
provided by EPA and WHO. Upon comparing the concentrations of our ions to that of these two
agencies, we are confident that all of the rivers within this study are well within the parameters
set by each respective agency. In most cases, our results from the ICP-MS compared to
Metals analysis of four Texas streams 16


regulations are different by an order of magnitude, if not more. The conductivity of the water is
also well within the range dictated by the EPA.