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Analyzing Five Salinity Determination Methods


Sharon Xu

Abstract
Salinity is a physical factor of water that refers to the amount of salt
there is dissolved in water. Five methods were used to determine the salinity of
a water sample in parts per thousand and then analyzed to determine which
method was the most accurate. The five salinity determination methods were
hydrometer, Knudsen Titration, refractometer, YSI 556 Meter, and evaporation.
There were no significant differences between the five methods, showing that
each method holds a degree of accuracy. For the higher salinity sample, the YSI
556 Meter was the most accurate and evaporation was the least accurate. For the
low salinity sample, a high variability was discovered among the salinity values
which made it difficult to determine which method was the most accurate
overall. To resolve this issue, a greater sample size is needed in any future
studies.

Introduction
Salinity is an important physical factor of water. It refers to the amount of salt there is
dissolved in water (Fondriest, n.d.). Multiple types of salt make up the sea salt found in seawater.
The common types are sodium chloride, NaCl; potassium chloride, KCl; magnesium chloride,
MgCl2; and calcium carbonate, CaCO3 (Millero, 2002). There are various methods to determine
salinity, some more accurate than others. Salinity determination methods are based on an
assorted range of properties including but not limited to specific gravity, light refraction,
conductivity, etc. Salinity can be measured in parts per thousand (ppt) or in practical salinity
units (psu) which are equivalent (Fondriest, n.d.). The measurement of salinity is important in
estuarine areas because it can help monitor the amount of saltwater or freshwater presence in a
particular area. In Barnegat Bay, salinity ranges from 19 ppt to 30 ppt with an average salinity of
25 ppt in the central bay (US Fish and Wildlife Service, n.d.). The lower salinities are found at
the mouths of rivers and creeks within the watershed such as Toms River and Cedar Creek. The
water at the inlets have greater salinities. It is important for the salinity of Barnegat Bay and
other water bodies to be monitored because some species can only survive in a narrow range of
salinities (Bochenek et al., 2001). To monitor the salinity of a body of water properly, the
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methods utilized must be accurate. This study was completed to determine which of the five
available methods to determine salinity was the most accurate.

Methodology
Study Area:
The data utilized in this study was obtained from a lab conducted in the Research
Methods & Applications class regarding salinity determination. Working with their groups from
field, the students explored five methods to determine salinity. Experimentation took place at the
Marine Academy of Technology on April 20, 2017. Two unknown salinity samples were
prepared by Dr. Wnek. One salinity sample was assigned to each group. Groups 2, 4, and 5 used
the salinity sample from the white container. Groups 1, 3, and 6 used the salinity sample from the
orange container. The actual salinity of the white container was 19.8 ppt while the actual salinity
of the orange container was 8.6 ppt.
Procedure:
Each group experimented with the five different salinity tests. The five methods are as
follows: hydrometer, refractometer, YSI 556 Meter, Knudsen Titration, and evaporation. All
measurements were reported in parts per thousand (ppt). The hydrometer (Figure 6) was placed
in the graduated cylinder filled with the sample water to determine specific gravity while a
thermocouple was used to measure temperature. A chart was then referenced to determine the
salinity that corresponds to the specific gravity and temperature of the sample. To determine
salinity using the Knudsen Titration method, the sample was first diluted with demineralized
water then titrated according to the directions on the test kit (Figure 7). For the refractometer
(Figure 8) a pipette was used to transfer the sample onto the refractometer’s daylight plate. It was
then aimed at a light source in order to determine the angle of refraction which corresponds to
the sample’s salinity. While using the YSI 556 Meter (Figure 9), the probe was placed in the
water sample until the reading stabilized. For the evaporation method (Figure 10), a crucible was
filled with 10 mL of the sample water and placed over a hot plate to evaporate the water while
leaving the salt behind. The crucible was placed in the desiccator to remove the moisture from
the sample and to cool down the sample prior to being measured. The mass of the crucible was
recorded before and after the evaporation using an analytical balance in order to determine the
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amount of salt there was in 10 mL of the sample water. The salinity of the sample in parts per
thousand was then calculated using those values.
Statistical Analysis:
An ANOVA single factor test was used to determine whether or not there were statistical
differences between the salinity values obtained using the five methods. Two tests will be used in
total, one for the groups with the 9.6 ppt salinity container and another for the groups with the
19.8 ppt salinity container. Depending on whether or not there was a statistical difference, post
hoc analysis can be completed on the salinity values using a Tukey test. This can be done to
determine which salinity method has readings that are different from the rest, if applicable. An
alpha values of 0.05 or less was used to determine significance.

Results
The experimentally determined salinity values for the white container (actual salinity =
19.8 ppt) ranged from 12.2 ppt to 20.9 ppt. The 12.2 ppt value, determined using evaporation, is
an outlier in the dataset. When comparing the salinity readings from the different methods using
an ANOVA test, the p-value was 0.056, indicating that the differences were not significant. The
salinity values for the orange container (actual salinity = 9.6 ppt) ranged from 7.0 ppt to 11.7 ppt.
The ANOVA test on the salinity readings had a p-value of 0.078, showing the data was not
significant.

Discussion
The ANOVA tests for the salinity readings obtained using five different methods showed
that the differences were not significant. See Figures 1 and 2. No differences were expected since
they all measure the same thing. The salinity values should be similar. A significant difference
would indicate that one or more of the methods were inaccurate. For the higher salinity sample,
the evaporation method provided the greatest variation in salinity readings with 7.3 ppt
separating the highest values and the lowest values (Figure 4). More so than the other methods,
salinity values obtained using evaporation are vulnerable to human error (Bureau of
Reclamation, n.d.). However, there still were no significant differences between the five
methods. The evaporation method was the least accurate in determining salinity. The average
salinity reading obtained from evaporation was 16 ppt compared to the actual value of 19.8 ppt,
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indicating a 19.2% error. From least accurate salinity method to the most accurate, they were
determined to be evaporation (19.2% error), refractometer (5.6% error), hydrometer (5.1%
error), Knudsen Titration (4.5% error) to YSI 556 (1.5% error) for the 19.8 ppt sample. See
Figure 5. The salinity readings from the YSI 556 had an average of 19.5 ppt which was only 0.3
ppt from the actual value and the most accurate out of the five salinity methods used.
The accuracy of each method on the lower salinity sample differed from that of the
higher salinity sample. The method that resulted in the closest reading to the actual value this
time was evaporation and the hydrometer. The range of values for the hydrometer was 8.9 ppt to
10.2 ppt (Figure 3). Only the average happened to be close to 9.6 ppt. Salinity values from
evaporation ranged from 7.7 ppt to 11.7 ppt (Figure 3). For the two methods, there were high
readings and low readings which created an average that came close to the actual value. This
causes the precision of the instrument to be called into question because the hydrometer and
evaporation are reporting both very high and low salinity values for the same sample of water.
They do not consistently report a salinity value that matches the actual value which prevents
them from being designated as the most accurate methods (Figure 3). The variability of the
salinity values is much greater for the lower salinity sample. The percent errors for the other
three methods were 13.5% for Knudsen Titration, 24% for the refractometer, 15.6% for the YSI
556. See figure 5. Based on percent error alone, the least accurate to most accurate are the
refractometer, YSI 556, Knudsen Titration, evaporation, hydrometer. Since the “most accurate”
salinity values are not at all consistent with each other, they are not a good representation of
salinity values obtained using that method. As a result, the findings are inconclusive as to which
method is the most accurate. In order to have a better ranking of accuracy, a larger sample size is
needed.
The YSI 556 Meter did not do as well with the lower salinity sample compared to the
high salinity sample. In this case, the average YSI 556 Meter salinity readings differed from the
actual value by 1.5 ppt for the low salinity sample compared to 0.3 ppt for the high salinity
sample. The values differ a lot for an instrument that is accurate within 0.1 ppt according to the
manufacturer (YSI Model 556 Operations Manual, n.d.). The YSI 556 Meter is the method with
the least room for human error. Its operating procedure is very simple which makes the dramatic
change in accuracy between the two samples very surprising. The change from 1.5% error for the
19.8 ppt salinity sample to 15.6% error for the 9.6 ppt salinity sample (Figure 5). Possible
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explanations could include calibration errors but even that does not the explain the enormous
accuracy differences. The YSI 556 Meter is known for being an accurate instrument. It measures
salinity by determining the conductivity of a water sample which is directly proportional to the
salinity (YSI Model 556 Operations Manual, n.d.). More salt ions in the water, the higher the
conductivity, the higher the salinity (YSI, n.d.). It is also possible that the meter is not at fault,
but that the groups with the lower salinity sample failed to mix the water before obtaining a
sample, resulting in some with higher salinities and others with low. According to its
manufacturer, La Motte, the salinity test kit used for Knudsen titration has a sensitivity of 0.4 ppt
(La Motte, n.d.). However, the salinity values obtained using Knudsen Titration had a high
variability that surpassed the 0.4 ppt and lead to readings with 13.5% error and 4.5% error. This
shows that the Knudsen Titration is susceptible to human error. The refractometer is less
accurate due to the difficulty associated with reading it correctly. It can be difficult to discern
where the blue and the white meet. Errors for a salinity value determined using evaporation may
be due to spillage when the crucible is held above the heat source. Water loss decreases the
amount of salt that was originally part of the sample, making the salinity value lower than it is
suppose to be. The evaporation method generated the greatest variability between values within a
single method (Figure 4). Differences between the salinity readings from the hydrometer and the
actual values can be attributed to the approximations that were done in using specific gravity and
temperature to find salinity (New Jersey Sea Grant Consortium, 2010). Overall, based on the
results of the high salinity sample testing, the YSI 556 Meter should have been the most accurate
method to determine salinity, but this was not completely supported by the data.

Conclusion
There were no significant differences between the five methods used to determine
salinity: hydrometer, refractometer, YSI 556 Meter, Knudsen Titration, and evaporation. For the
higher salinity sample, the most accurate was the YSI 556 Meter, and the least accurate was
evaporation. An accuracy ranking could not be determined for the lower salinity sample. Finding
the most accurate salinity determination method is important because using a flawed method can
lead to faulty readings that misrepresent the water quality.

References
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Bochenek, E. A., Bognar, J. A., Evenson, E., Griber, P., Hunchak-Kariouk, K., Jivoff, P., . . .
Westfall, G. J. (2001). The Scientific Characterization of the Barnegat Bay-Little Egg
Harbor Estuary and Watershed . Retrieved from
http://bbp.ocean.edu/Reports/The%20Scientific%20Characterization%20of%20the%20B
arnegat%20Bay-Little%20Egg%20Harbor%20Watershed.pdf
Bureau of Reclamation. (n.d). Salinity and Total Dissolved Solids. Retrieved April 26, 2017
from
https://www.usbr.gov/lc/phoenix/programs/cass/pdf/Phase1/ATechapdxTDS.pdf
Fondriest. (n.d.) Conductivity, Salinity & Total Dissolved Solids. Retrieved April 26, 2017 from
http://www.fondriest.com/environmental-measurements/parameters/water-quality/conduc
tivity-salinity-tds/
La Motte. (n.d.). Salinity Test Kit. Retrieved April 26, 2017, from
http://www.lamotte.com/en/education/water-monitoring/education-kits/7459-02.html
Millero, F. J. (2002). Sea Water as an Electrolyte. Chemistry of Marine Water and Sediments,
3-34. doi:10.1007/978-3-662-04935-8_1
New Jersey Sea Grant Consortium. (2010). Salinity. Retrieved April 27, 2017 from
http://www.njseagrant.org/wp-content/uploads/2014/03/salinity.pdf
US Fish and Wildlife Service. (201.). Barnegat Bay Complex. Retrieved April 25, 2017, from
https://nctc.fws.gov/pubs5/web_link/text/bbc_form.htm
YSI. (n.d). Conductivity. Retrieved April 27, 2017 from
https://www.ysi.com/parameters/conductivity
YSI Model 556 MPS Operations Manual. (n.d.). Retrieved from
https://www.ysi.com/File%20Library/Documents/Manuals/655279-YSI-556-Operations-
Manual-RevD.pdf
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Figure 1: Salinity values (in ppt) for this water sample were determined using five
methods. The average salinity readings from the three groups were used. The
p-value was 0.0785, showing that the data was not significant. Since the
differences between the five methods were not significant, this indicates that each
method holds a degree of accuracy. Bars indicate ±5% values of the mean.

Figure 2: Five methods were used to determine the salinity value (in ppt) for this
water sample. The three groups’ salinity readings were averaged. The p-value was
0.056, showing the data was not significant. Each method holds a degree of accuracy
since there were no significant differences. Bars indicate ±5% values of the mean.
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Figure 3: Three groups were assigned to each water sample. Salinity values
(in ppt) for this water sample were determined using five different methods.
The salinity readings had a high variability within a method especially the
ones obtained using evaporation. High variability among values that should
be the same can indicate an inconsistent or malfunctioning meter or user error. The
refractometer readings had the least variability.

Figure 4: Three groups were assigned to each water sample. Five different
methods were used to determine salinity values (in ppt). The salinity readings
obtained from evaporation had a high variability. This is likely due to spillage
while evaporating the saltwater. The hydrometer readings had the least variability.
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Figure 5: The salinity method that generated the most accurate value was
different depending on whether it was based on the 9.6 ppt sample of the 19.8 ppt
sample. The most accurate method for the 9.6 ppt sample was tied between the
hydrometer and evaporation. For the 19.8 ppt sample, the most accurate method
Was the YSI 556. In both samples, the hydrometer was the only method that
overestimated the true salinity value. All other methods consistently
underestimated the salinity.

Figure 6: A student using a thermocouple to


measure the temperature of the water which
affects salinity. The hydrometer can be seen
inside the graduated cylinder.
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Figure 9: The YSI 556 measures salinity


Figure 8: A student looking through the based on the conductivity of the water
eyepiece of a refractometer which measures sample.
salinity based on the angle of refraction.

Figure 7: A student using Knudsen titration Figure 10: A crucible filled with 10mL of
to determine salinity. She is slowly the sample water is being evaporated so all
dispensing Salinity Titration Reagent B until that remains is the salt. The difference
the color becomes pink-brown at which time between the mass before and after
the value can be recorded as ppt Salinity. evaporation is used to calculate the salinity.
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