# Presentation: 110475

##     Ammonia modeling for assessing toxicity to fish species in the Rio Grande, 1989-2002 

**    ****Ammonia modeling for assessing toxicity to fish species in the Rio Grande, 1989-2002 **

**Howard D. Passell**
** ****Sandia National Laboratories Geosciences and Environment Center **
**Clifford N. Dahm**
** ****University of New Mexico Dept. of Biology**
** ****Edward J. Bedrick**
**University of New Mexico Dept. of Math and Statistics**

## Data from USGS stations at Albuquerque and Isleta, and from SSWRP, 1989-2002
We used system dynamics modeling to mix daily values for:
discharge, temperature, pH and N-NH4+ in SSWRP effluent
with discharge, temperature, and pH in the Rio Grande
to generate NH3 concentrations in the Rio Grande

- Data from USGS stations at Albuquerque and Isleta, and from SSWRP, 1989-2002
- We used system dynamics modeling to mix daily values for:
- discharge, temperature, pH and N-NH4+ in SSWRP effluent
- with discharge, temperature, and pH in the Rio Grande
- to generate NH3 concentrations in the Rio Grande

- _Study area_

- _Methods_

***What role has toxic ammonia derived from Albuquerque’s sewage effluent played in the endangerment of the Rio Grande silvery minnow?***

## SSWRP pH

- _Rio Grande pH_

- We have daily discharge data from both the SSWRP and the Rio Grande for the entire study period, but . . .

## SSWRP Temp

- _Rio Grande Temp_

## SSWRP N-NH4+

## Addressing uncertainty in the data

- Besides NH4+, pH data are most critical
- After various sensitivity analyses, we made
- 60 sets of SSWRP pH data, using mean and SD from existing data
- 60 sets of Rio Grande pH data using different means and different SDs for different years
- We ran the model 60 times, with a different set of SSWRP pH data and a different set of Rio Grande pH data in each run, and then aggregated the results

## Model results: NH3 concentrations averaged from 60 model runs

## Model results: mean exceedences

## Model assumptions

- Equilibration between SSWRP and Rio Grande hydrogen ion, temperature and NH4+/NH3 is rapid and complete
- No losses of NH4+ occur
- 1. Biological uptake –bryophytes, algae, bacteria, fungi
- 2. Adsorption to organic materials in sediments
- 3. Nitrification
- No losses of NH3 occur through volatilization
- Half of a concentration of NH3 in the Rio Grande will volatilize over about **2 - 6 km**, using estimated reaeration coefficients for oxygen (K2 = 5 - 15), and assuming flow rate of 0.5 m/s
- 			(NH3)t = (NH3)0e-K2t
- NH3-N is modeled for 81 days from 1989-1992; values exceed 0.2 mg/L (2 x 0.10 mg/L) on 8 days, or 10 percent of the time. Assuming rapid and complete mixing, chronic conditions (i.e., >0.10 mg/L NH3-N) would have extended 2 - 6 km downstream of the SSWRP 10 percent of the time

- Eq. 3

## Model assumptions -- 2

- No losses from combined NH4+/NH3 removal
- AMMTOX 2 (Lewis *et al.*, 2002) applied to the Rio Grande suggests that half a concentration of total ammonia (NH4+/NH3) will be removed by all processes over **3-5 km**, using estimated K values of 6 – 10.2
- 					(NH3)t = (NH3)0e-K2t
- No additions of NH4+ and NH3
- Rio Rancho and Bernalillo (sewage and spills = 4ML in 2000, + Cl)
- No rising trend in Rio Grande pH considered
- pH rose at Isleta from 7.9 in 1975 to 8.1 in 1999
- At pH 7.9, 10 mg/L N-NH4+ equilibrates to about **0.42** mg/L N-NH3 (at 25 degrees C)
- At pH 8.1, 10 mg/L N-NH4+ equilibrates to **0.67** mg/L N-NH3 (at 25 degrees C)

- Eq. 4

## Model assumptions -- 3

- No mixing of toxicants
- Buhl (2002) tested toxicity to silvery minnow and fathead minnow in a mix that simulated the water of the Rio Grande
- Chlorine in the MRG was most toxic – 96-hr LC50 0.114 mg/L
- Copper was second – 96-hr LC50 0.250 mg/L
- NH3 was third – 96-hr LC50 1.0 mg/L
- Copper and NH3 accounted for 93-98% percent of toxicity, and toxicity was more than additive
- Chronic criterion could be as low as 0.001 mg/L N-NH3, based on the mix
- Site specific acute and chronic criteria might be appropriate for the Rio Grande

## Rio Grande silvery minnow, once one of the most common fish in the Rio Grande is now limited to about 5% of its former range, between Cochiti Dam and Elephant Butte Dam
Four other cyprinids were made extinct or extirpated from the Rio Grande (3/4 in the last 40 years)
Extirpated
Rio Grande shiner (Notropis jemezanus) last collected between 1901 and 1950
Speckled chub (Extrarius aestivalis), last collected in 1960s
Extinct
Phantom shiner (Notropis orca), last collected in 1964
Bluntnose shiner (Notropis simus simus), last collected in 1975
EPA acute criteria for N. spilopterus and N. whipplei are less than 1⁄2 the acute criterion for the fathead minnow 
Notropis may be a genus generally more sensitive to NH3

- Four other cyprinids were made extinct or extirpated from the Rio Grande (3/4 in the last 40 years)
- Extirpated
- Rio Grande shiner (*Notropis jemezanus*) last collected between 1901 and 1950
- Speckled chub (*Extrarius aestivalis*), last collected in 1960s
- Extinct
- Phantom shiner (*Notropis orca*), last collected in 1964
- Bluntnose shiner (*Notropis simus simus*), last collected in 1975
- EPA acute criteria for *N. spilopterus* and *N. whipplei* are less than 1⁄2 the acute criterion for the fathead minnow
- Notropis may be a genus generally more sensitive to NH3

- _What is the relevant ecological history of Rio Grande fish community? _

## Relevant criteria for NH3-N

- LC50 NH3-N concentrations for fish over many studies range from 0.06 mg/L at 72 days to 2.55 mg/L at 96 hours
- Silvery minnow: 96-hr LC50 1.01-1.12 mg/L (Buhl, 2002)
- EPA fathead minnow chronic value: 0.17 mg/L (adopted by USFWS for the silvery minnow)
- NM and EPA chronic derivation: 10% of known LC50 value, if toxicant is non-bioaccumulating (= 0.10 mg/L, based on Buhl, 2002)
- NM acute criterion for warm water fisheries = 0.30 mg/LNM chronic criterion for warm water fisheries = 0.05 mg/L
- Chronic criterion for fish, including embryos, larvae, juveniles and adults, over many studies range from 0.001 to 0.71

## Model results, again: daily NH3-N concentrations

- _Model results, again: daily NH__3__-N concentrations_

## Model results, again: Exceedences

- _Model results, again: Exceedences_

## 
NH3 concentrations may have been high for decades prior to 1989
NH3 contributed to the extirpation and extinction of native cyprinids
NH3 contributed to the current endangerment of the silvery minnow (along with other causes)

Improvements at the SSWRP resulted in 2002 average NH3-N concentrations of 0.0004 mg/L, but NH3 could still pose a threat with:
Increasing populations upstream and downstream of Albuquerque
Accidental spills
Synergistic effects of mixed toxicants

Declining water quality is a hidden consequence of drought in effluent-influenced streams

- NH3 concentrations may have been high for decades prior to 1989
- NH3 contributed to the extirpation and extinction of native cyprinids
- NH3 contributed to the current endangerment of the silvery minnow (along with other causes)
- Improvements at the SSWRP resulted in 2002 average NH3-N concentrations of 0.0004 mg/L, but NH3 could still pose a threat with:
- Increasing populations upstream and downstream of Albuquerque
- Accidental spills
- Synergistic effects of mixed toxicants
- Declining water quality is a hidden consequence of drought in effluent-influenced streams

- _Conclusions_

## NH3 toxicity may have created a barrier to silvery minnow migration in the Rio Grande. Success of current plans to create minnow refugia upstream of Albuquerque may be enhanced by the removal of that barrier

NH3 toxicity could be playing a large role in rivers around the world, especially in developing nations where sewage treatment is limited or absent.

- NH3 toxicity may have created a barrier to silvery minnow migration in the Rio Grande. Success of current plans to create minnow refugia upstream of Albuquerque may be enhanced by the removal of that barrier
- NH3 toxicity could be playing a large role in rivers around the world, especially in developing nations where sewage treatment is limited or absent.

- _Conclusions -- 2_