Robert Olsen
ES 220
05/05/05

Palouse Fall Water Quality Internship

 

Previous Internship work

There have been three previous internships dealing with pollution in the Palouse River; however, none of them have analyzed the River over an extended amount of time. Marieke analyzed nitrogen based pollutants – nitrite, nitrate, and ammonia -- with one sample. Elizabeth and Miranda analyzed data from the USGS and the Washington State Department of Ecology, but as they point out the USGS data is collected once a decade and that the DOE was not very helpful. Neither Marieke nor Elizabeth and Miranda found a source for pollution. Hunter took up where they left off and tried to find a source for nitrate, nitrite, and phosphate in the River. A potential non-point source for pollution is a small farm located about ¾ of a mile upstream from the falls. Hunter took one sample and analyzed it for nitrate, nitrite, and phosphate; however, by only analyzing one sample he was unable to view any trends or determine if pollution was very prevalent. In order to improve on the studies of the previous interns, it is imperative that I sample multiple times for both nitrogen-based pollutants – nitrite, nitrate, ammonia – and phosphorous.


My Work

During my initial meeting with Sandra Cannon, we discussed what could be done to improve on the previous interns. We came up with taking multiple samples in the spring (peak water levels) and analyzing them for nitrogen and phosphate. We came up with three goals:


1) Find farm hunter mentioned in his paper

2) Sample above and below farm multiple times to find trends and possible source for pollution

3) Determine if the farm is a point source


In order to find the farm Hunter mentioned and to take water samples it is imperative that the intern have a means of transportation to and from the falls. Palouse Falls is located about 65 miles away from Walla Walla, so the intern must be willing to spend a significant amount of time driving. Besides driving, there is a large amount of hiking/walking involved. The farm is located about 1 mile (farther than Hunter suspected, Figures 1 and 2) upstream; however, the walk seems longer because hiking is done along the railroad tracks. Eventually, the ravine slopes along the left side of the river turn into cliffs; making decent to the river nearly impossible. Water samples have to be collected about 1/8 mile downstream from the farm. I was unable to get to the upper side of the farm because it was another few miles along the railroad tracks, and the minimal use of the land for the farm suggested it was not adding substantial nitrates, phosphates, or nitrites into the water.

 

 

Figure 1: The farm Hunter located about ¾ of a mile upstream of Palouse Falls.

 

Figure 2: The farm is on the nearly level ground within the red square. Each black square on the map is 1x1 Km.

 


Findings

The closest Department of Ecology monitoring site to Palouse Falls is in Hooper, WA, about 27 miles upstream. At this long term monitoring station, samples have been monitored since 1959 with very few recorded exceedences of nitrate, nitrite, and phosphate since then (exceedences regarding DOE’s definitions). According to Hunter’s data from Palouse Falls there were no exceedences in the fall of 2004. Total nitrogen concentrations (nitrate + nitrite concentrations) above Palouse Falls were lower than those levels at Hooper. The Hooper levels on October 5, 2004 were 1.83 mg/L, whereas Hunter’s totals were 1.524 mg/L, indicating that pollution occurring between Hooper and Palouse Falls either did not exist, or was minimal enough to be diluted.

This winter, the water quality in the Palouse was better than in most years (Table 1 and Table 2). The phosphate levels at Hooper were within the acceptable range (as designated by the DOE) and followed historical trends. However, the same cannot be said for total nitrogen concentrations. This winter was unique, total nitrogen concentrations did not follow historical trends; they were significantly lower than most years. In 2004, the concentrations were 6.87 mg/L, and 6.57 mg/L for February and March, respectively. This year the concentrations were 1.99 mg/L and 0.915 mg/L for February and March, respectively.

The two times I went to Palouse falls I went immediately after rainstorms. The water had become a milky brown color from high sediment concentrations. It is very possible that during the rainstorms, nitrate, nitrite and phosphate were washed from the surrounding hillsides into the tributaries of the Palouse River and directly into the Palouse. The concentrations of nitrogen and phosphorous I found at Palouse Falls, collected on April 3 and April 10 were: 7.45 mg/L and 7.24 mg/L for nitrogen and 1.21 mg/L and 0.89 mg/L. (I analyzed the Palouse water samples using an Ion Chromatograph in the environmental chemistry lab at Whitman College, and determined ion concentrations using a Linear Least Squares Microsoft Excel spreadsheet designed by Frank Dunnivant.) This contrasts with April 14, 2004 levels at Hooper of 0.991 mg/L total nitrogen and 0.0469 mg/L total phosphorous concentrations (DOE website). Even though the samples I analyzed indicated high levels of nitrate, the concentrations were still well below the EPA Maximum Contaminant Level (MCL). Nitrate was present at an about 5.75 mg/L, which is 4.25 mg/L less than the 10 mg/L MCL of the EPA. Unfortunately, nitrite was present at about 1.5 mg/L, which is 0.5 mg/L higher than the MCL of the EPA. And phosphate levels were about 1 mg/L, but the EPA does not have a listed MCL for phosphate. The health effects and Malls of phosphate can be found in Table 3.

The increase in nitrogen and phosphate concentrations is most likely due to the heavy rainstorms and not the farm that Hunter found. The farm Hunter found is not a non-point source of pollution. When I examined the farm from a cliff side about 1/5 mile away the shore was missing vegetation, but that fact seemed irrelevant. There were cattle as Hunter indicated, but only a few. I spotted a total of 5 cattle on probably 20 acres. It also seems unlikely that cattle use the water frequently, there were no paths worn into the grass towards the river, and there was a small gully between the farm and the river. Besides cattle, agricultural activity was not occurring. There were no sprinkler systems nor was there any equipment used to harvest crops (Figure 1). These facts lead me to believe that the levels of nitrate, nitrite, and phosphate present in the Palouse River above Palouse Falls are not due to the farm that Hunter found, but instead residual pollution from upstream agriculture.


Reflections

On my first trip to the Palouse River, the water was clear, except at the base of the falls. At that time, I assumed the river clean, but only the pool was dirty because of the clear river and the green algae at the base of the falls. After looking at Hunter’s data, I changed my assumption; the water was nearly free of pollutant anions, but as it fell nearly 200 feet nitrogenation occurred. Now that I have analyzed my own samples from water with sedimentation, I believe the contamination is a mixture of human and natural causes. This thought process indicates that the internship with Sandra Cannon is beneficial, even if the samples prove a lack of anions in the water. I am grateful to have been able to critically examine assumptions I made about the river.

Besides thinking critically the internship was somewhat difficult. Initially, neither Hunter, nor Penrose library had maps that would help me locate the farm Hunter had mentioned in his paper. The first time I traveled to Palouse Falls I was unable to find the farm, even after hiking nearly a mile along the river. The second time I went to the fall; I hike more than a mile along the railroad tracks, and climbed the embankments along its edge until I encountered Hunter’s farm. It is located about 1 aerial km, or 2 hiking km, upstream from the falls. I used a 200mm zoom on a Minolta camera to look more closely at the farm. Having a pair of binoculars would have been extremely useful.

After collecting samples, I spent nearly 20 hours in the lab using the ion chromatograph (IC). At first, the mobile phase was too old to work in the IC. And then I accidentally left the helium gas on, which meant I could not take analyze samples until I obtained a new tank of helium. Ultimately, this experience taught me that sometimes it is better to sacrifice highly precise measurements (the IC) for something mobile and fast (a HACH kit).

Lastly, when I presented my poster to Bob, I had assumed that the high levels of anions, shown in T
able 2, were an indication an error on my part. But while writing this report I looked more closely at the finalized historical data on the DOE website and at times it had higher concentrations than my samples. This was just another indication of the need to always think critically about the work being done, the data itself, and the interpretations of that data.


Recommendations

The most polluted looking section of the Palouse River was below Palouse Falls. The water was green with what is potentially an alga. Future interns should look into the pollution present above and below the falls. Interns should look for specifically for pollution containing nitrate, nitrite, and phosphate because of their potential for eutrophication. Future interns should use mobile HACH Kits to determine ion concentrations because of their ease of use, and on site capabilities. While examining the water below the falls, the intern should examine the prevalence and species of algae present. These possibilities give future interns a broad range of information but also help them determine if pollution is actually detrimental to the river system. If interns discover pollution, they should try and more find point sources and develop methods for talking with agriculturists.



Key Contacts

Sandra Cannon
803 Valencia St.
Walla Walla, WA
(509) 525-8849
sandra.cannon@pnl.gov

Frank Dunnivant
Assistant Professor of Chemistry
Hall of Science 344
526-4751
dunnivfm@whitman.edu

The Environmental Protection Agency’s Maximum Contaminant Level (MCL) website.
http://www.epa.gov/safewater/mcl.html#mcls


Department of Ecology Contacts:
Jim Ross, Environmental Assessments Program Freshwater Monitoring Unit/ERO
JROS461@ECY.WA.GOV
(509) 329-3425
(509) 953-0177 mobile
(509) 329-3529 FAX

Chris Coffin (CCOF461@ecy.wa.gov) is monitoring that site (Hooper).

Elaine Snouwaert(ESNO461@ecy.wa.gov) is the lead for the upcoming TMDL studies in the watershed.

The Washington Department of Ecology, Long term monitoring of the Palouse River. http://www.ecy.wa.gov/apps/watersheds/riv/station.asp?theyear=&tab=notes&scrolly=0&wria=34&sta=first


Other Resources

Adams County Conservation District is doing a lot of monitoring on tribs to the Palouse and on the mainstem. Their email is adamcd@ritzcom.net.
Feel free to contact me if you need more information


Tables and Figures

Table 1: Data from the Department of Ecology on Nitrogen and Phosphorous Concentrations from February and March of 2004 and 2005.

Date
Phosphorous
Total Nitrogen
(mg/L)
(mg/L)
2/11/2004

0.128

6.87
3/10/2004
0.133
6.57
2/8/2005
0.102
1.99
3/8/2005
0.0385
0.915

 

Table 2: A comparison of data collected at Hooper, WA on 3/8/2005 with data collected on 4/3/2005 and 4/10/2005.

Palouse River Anion Concentrations (mg/L)
Hooper*
Palouse Falls (4/3)
Palouse Falls (4/10)
T Nitrogen
0.915
T Nitrogen
7.45
T Nitrogen
7.24
T Phosph.
0.0385
T Phosph
1.21
T Phosph
0.89
*Preliminary data from 3/8/2005      

 

Table 3: The maximum contaminant levels, sources and health effects of phosphate, nitrate, and nitrite.

Contaminant
MCL*
Health Effects
Sources
Nitrate (measured as Nitrogen 10 Infants below the age of six months who drink water containing nitrate in excess of the MCL could become seriously ill and, if untreated, may die. Symptoms include shortness of breath and blue-baby syndrome. Runoff from fertilizer use; leaching from septic tanks, sewage; erosion of natural deposits
Nitrite (measured as Nitrogen 1 Infants below the age of six months who drink water containing nitrite in excess of the MCL could become seriously ill and, if untreated, may die. Symptoms include shortness of breath and blue-baby syndrome. Runoff from fertilizer use; leaching from septic tanks, sewage; erosion of natural deposits
Phosphate** ------- Kidney patients at increased risk of premature death Runoff from fertilizer use; leaching from septic tanks, sewage; erosion of natural deposits
*maximum contaminant level  
**Not from the EPA, but Nitrate and Nitrite are  




Table 4: Linear Least Square Analysis of Nitrate          
                   
NITRATE                  
Linear Least Square Analysis              
Number of Standard Observations= 4            
Replicates for Sample Unknowns= 3            
Units of Standard=   mg/L            
Number x-Value y-Value xy x-squared y-squared        
  Conc. Signal              
1 0 0 0 0 0        
3 1 276684 276684 1 7.66E+10        
4 2 401877 803754 4 1.62E+11        
5 5 4989133 24945665 25 2.49E+13        
Sums 8 5667694 26026103 30 2.51E+13        
Means 2 1416923.5              
                   
  Sxx= 14 Sum of Squared Error for the mean of x      
  Syy= 1.71E+13 Sum of Squared Error for the mean of y      
  Sxy= 1.47E+07 Sum of Squared Error for x and y      
  m= 1.05E+06 Slope            
  b= -6.82E+05 y-intercept          
  Sr = 9.17E+05 Standard Deviation of the Residuals      
  Sm= 2.45E+05 Standard Deviation of the Slope        
  Sb= 6.71E+05 Standard Deviation of the Intercept      
  r = 0.948              
 

r2=

0.898              
                   
Unknowns Signal   Signal   Signal   sc= std.dev. of an unknown
3-Apr Rep 1 Conc 1 Rep 2 Conc 2 Rep 3 Conc 3 Means
Abs.
Mean
mg/L
sc
Nitrate 5602131 5.99 5488677 5.88 5784186 6.16 5624998 6.01 1.15
10-Apr                  
Nitrate 5176064 5.58 4725725 5.15 5913210 6.28 5271666 5.67 1.09


 

Table 5: Linear Least Square Analysis of Nitrite          
                   
NITRITE                  
Linear Least Square Analysis              
Number of Standard Observations= 4            
Replicates for Sample Unknowns= 3            
Units of Standard=   mg/L            
                   
                   
Number x-Value y-Value xy x-squared y-squared        
  Conc. Signal              
1 0.01 54404 544.04 0.0001 2.96E+09        
3 0.1 3279838 327983.8 0.01 1.08E+13        
4 0.5 2523976 1261988 0.25 6.37E+12        
5 1 4493827 4493827 1 2.02E+13        
Sums 1.61 10352045 6084343 1.2601 3.73E+13        
Means 0.4025 2588011.25              
                   
  Sxx= 1 Sum of Squared Error for the mean of x      
  Syy= 1.05E+13 Sum of Squared Error for the mean of y      
  Sxy= 1.92E+06 Sum of Squared Error for x and y      
  m= 3.13E+06 Slope            
  b= 1.33E+06 y-intercept          
  Sr = 1.50E+06 Standard Deviation of the Residuals      
  Sm= 1.92E+06 Standard Deviation of the Slope        
  Sb= 1.08E+06 Standard Deviation of the Intercept      
  r = 0.887              
 

r2=

0.787              
                   
Unknowns Signal   Signal   Signal   sc= std.dev. of an unknown
3-Apr Rep 1 Conc 1 Rep 2 Conc 2 Rep 3 Conc 3 Means
Abs.
Mean
mg/L
sc
Nitrite 5274976 1.26 5939162 1.47 6299885 1.59 5838008 1.44 0.73
10-Apr                  
Nitrite 6429088 1.63 5373005 1.29 6889699 1.78 6230597 1.57 0.80



Table 6: Linear Least Square Analysis of Phosphate          
                   
PHOSPHATE                  
Linear Least Square Analysis              
Number of Standard Observations= 4            
Replicates for Sample Unknowns= 3            
Units of Standard=   mg/L            
                   
                   
Number x-Value y-Value xy x-squared y-squared        
  Conc. Signal              
1 0.05 32307 1615.35 0.0025 1.04E+09        
3 0.1 935458 93545.8 0.01 8.75E+11        
4 0.5 1468245 734122.5 0.25 2.16E+12        
5 1 2861109 2861109 1 8019E+12        
Sums 1.65 5297119 3690393 1.2625 1.12E+13        
Means 0.4125 1324279.75              
                   
  Sxx= 1 Sum of Squared Error for the mean of x      
  Syy= 4.20E+12 Sum of Squared Error for the mean of y      
  Sxy= 1.51E+06 Sum of Squared Error for x and y      
  m= 2.59E+06 Slope            
  b= 2.57E+05 y-intercept          
  Sr = 3.93E+05 Standard Deviation of the Residuals      
  Sm= 5.15E+05 Standard Deviation of the Slope        
  Sb= 2.89E+05 Standard Deviation of the Intercept      
  r = 0.981              
 

r2=

0.962              
                   
Unknowns Signal   Signal   Signal   sc= std.dev. of an unknown
3-Apr Rep 1 Conc 1 Rep 2 Conc 2 Rep 3 Conc 3 Means
Abs.
Mean
mg/L
sc
Phosphorous 3178360 1.13 3286366 1.17 3699208 1.33 3387978 1.21 0.20
10-Apr                  
Phosphorous 2603230 0.91 2228651 0.76 2859400 1.01 2563760 0.89 0.15




Figure 3: Retention times for phosphorous, nitrate, and nitrite in an ion chromatograph.