Ammonia monitoring
From: Brian Soenen [mailto:Brian.Soenen@dnr.state.ia.us]
Sent: Monday, July 11, 2005 3:14 PM
To: Volunteer water monitoring
Subject: [volmonitor] Volunteer Programs and Ammonia Monitoring
Greetings from Iowa!
I am wondering if anyone could provide me with some information on
ammonia monitoring. We'd really like to improve the IOWATER program by
adding ammonia as a parameter, but would first like to find a
monitoring
kit that satisfies a couple requirements:
1) Field kits - Any kit we choose to adopt must be a field kit - i.e.,
results are obtained in the field at the monitoring site. Most of our
current kits for our other parameters use test strips and/or color
comparators.
2) Ease of use - The easier to use the better
3) Reliable data - When dealing with easy-to-use field kits, data
quality is sometimes compromised. We conduct side-by-side monitoring
with all of our kits and professional methods to ensure data quality,
but it would be nice to know which kits not to spend our money/time
on.
4) Non-hazardous wastes - We are not interested in kits that yield
heavy metals and/or pose any other disposal or health issues.
5) Inexpensive - The cheaper the better
Any ideas/suggestions you can send will be greatly appreciated.
Thanks!
Brian Soenen
IOWATER Coordinator
3625 Nebraska Street
Sioux City, IA 51104
515.205.8587 (cell)
Brian.Soenen@dnr.state.ia.us
www.iowater.net
www.iowaprojectaware.com
Responses
>>> "Chris Sullivan" <chris.sullivan@po.state.ct.us>
7/11/2005 2:30 PM
Hi Brian,
How are you doing? For Project SEARCH we utilize Lamotte Colorimetric
analysis using the Nesslerization method, but this does generate mercury
waste, so dont try that one.
I also coordinate a volunteer program in my spare time that uses Hach
Pocket Colorimeter for ammonia anlaysis. The colorimeter is electronic
so costs are higher but more reliable and precise than the color wheel
option offered by Hach.
Here is a link to the product we use.
http://www.hach.com/hc/search.product.details.invoker/PackagingCode=5870040/
NewLinkLabel=Ammonia%2C+Pocket+Colorimeter+II/PREVIOUS_BREADCRUMB_ID=HC_SEAR
CH_KEYWORD/SESSIONID|BkV4TWpFeE1EazFOek15TmpNbVozVmxjM1JJVnc9PUFsaE9Veg==|
like I said it is a little pricey, but my volunteers (mostly retired
folk or high school students) have no problems using the equipment or
reagents.
I am pretty sure there is no mercury generated in this process either,
so that is beneficial for you as well.
Good luck with your quest!!
peace
chris
Chris Sullivan
Project SEARCH Coordinator
(203) 734-2513
FAX 203-922-7833
www.sciencecenterct.org/projectsearch
Center for Environmental Research Education
Kellogg Environmental Center
500 Hawthorne Ave
Derby, CT 06418
>>> Kris Stepenuck <kris.stepenuck@ces.uwex.edu> 7/11/2005 3:01 PM >>>
Hi Brian-
For rough scale stuff, we have the volunteers use the Hach test strips.
We
expect them to find no ammonia based on specificity of the test strips,
and
if they do find some positive result, then we follow up with a grab
sample
that gets shipped to a lab.
Here is the catalog number for the strips we use: Test Kit, Ammonia
Test
Strips, 0-6 ppm, 25 tests Cat# 2755325
Kris
>>> Phil Emmling <emmling@engr.wisc.edu>
7/11/2005 3:32 PM >>>
Brian,
I will look at my kits for ammonia. I made analytical standards and
tried 3 or 4 kits. The best kit I found was a cheap cube from either
Hach or LaMotte. The test uses salicylate. The kit was the least
toxic, needed the least time for color development (1 minute), and seemed to be able to tell normal (~0.050ppm) from problem (>1.000)
concentrations. I did not like the color wheels or comparators. I had
a
problem using the same glassware for nitrate-nitrite for ammonia in a
color comparator because the nitrate test converted N03 to ammonia and
was higher 1-10ppm than the usual ammonia range of 0.025-0.100. I
actually used 50% sulfuric acid to rinse the plastic tubes and later
used glass tubes. The basic reagents in the Cd reduction N03 test
stuck
to the plastic tubes more than the glass.
You should buy a kit and try to make it work with analytical standards
or ammonia added to real samples having ammonia to see if you can make
it work before turning it over to volunteers. Chemetrics has a low
and
a high range test. The low does increments of 0-1.0 and the high does
0-10. I would bet that the 0-1.0 tests are hard to distinguish and
reproduce but most samples will be less than 1.0. It would be good to
do pH on the samples since NH3 is toxic to fish and NH4 is not toxic
but
both will be analyzed with any test. At pH 9.3 1/2 will be in each
form. At higher pH NH3 will dominate and at lower pH (most of the
time)NH4 will dominate. The range around the 50% each mark of 9.3
(isoelectic point)is about 1 pH unit. At pH 10.3 about 100% will be
NH3
and lower than 8.3 100% will be NH4. There are tables for estimating
each form if you know the pH.
I will get back to you tomorrow with the kits I played with.
Phil Emmling
Environmental Chemistry & Technology Program
660 N. Park St.
Madison, WI 53706
Phone: 608 262-2899
FAX: 608 262-0454
>>> "Petersen, Gordon" <GPeterse@hach.com>
7/12/2005 5:44 PM >>>
Mr.. Soenen,
Your message was forwarded to me. My name is Gordon Petersen and I am
with the Hach Company and I am located in central Iowa.
I would recommend salicylate chemistry with a color disc wheel or
Pocket
Colorimeter II. The color disc wheel is catalog #24287-00 and measures
up to 2.5 mg/L. The PC II is 58700-40. You will probably prefer the
color disc wheel because of the price and non-hazardous chemicals.
Let us know if you have further questions. You can contact sales or
tech support at 800-227-4224 or leave me a message at ext. 2112.
>>> Phil Emmling <emmling@engr.wisc.edu>
7/27/2005 8:35 AM >>>
OK. I ordered several kits and settled on 2 but I honestly can't
remember why. The standard is made for 1 mg/L N. It might be useful
to
remember that pH determines the % that is likely to be NH3 versus NH4.
There are tables with the values. The 50% point is pH 9.3 and
generally
1 pH unit either side determines whether 100% is one form or the
other.
At pH 10.3 100% should be in the toxic to fish NH3 species while at pH
8.3 100% should be in the NH4 form. Since most streams are between
7.5-8.9 a lot is NH4. I don't know what the situation is for an
anhydrous ammonia spill or liquid manure slug. I assume these are
undiluted plumes that can be toxic and the pH is probably alkaline.
Phil Emmling
Environmental Chemistry & Technology Program
660 N. Park St.
Madison, WI 53706
Phone: 608 262-2899
FAX: 608 262-0454
>>> Phil Emmling <emmling@engr.wisc.edu>
7/27/2005 8:58 AM >>>
Brian,
Here is a Website that I found for testing aquarium water
http://www.novalek.com/kpd52.htm. The hobby people can be a good
source
of information about water chemistry that can be useful to citizens.
This looks like the cube that I have at home. I don't see any mention
of carryover from test to test. There is a link to a table for pH and
temperature considerations and mention of 0.6ppm total ammonia being
toxic to aquarium fish. The ammonia standard of 1 mg/L N is
equivalent
to 1.22mg/L as NH3 if all the N in the test is NH3. There is a nice
example at the bottom of the table for calculating NH3 at pH 7 and 18C
at a total ammonia concentration of 0.8 mg/L.
Phil Emmling
Environmental Chemistry & Technology Program
660 N. Park St.
Madison, WI 53706
Phone: 608 262-2899
FAX: 608 262-0454
>>> Phil Emmling <emmling@engr.wisc.edu>
7/27/2005 9:15 AM >>>
Brian,
I used the table to make a calculation of toxic NH3. If we measure
0.8mg/L with a kit at pH 8.3 and 20C (conditions in a lot of stream
for
pH and T) the factor is 0.0736 from the table. 0.8mg/L x 0.0736 is
0.058mg/L N as NH3. If we subtract 0.058 from the total measured N of
0.08 we have 0.742 mg/L N as NH4. I calculate 92.6% N as NH4 and 7.4%
N
as NH3. I think we need to take the 0.058mg/L N as NH3 and convert it
to NH3 by multiplying by 1.22 or 0.058 x 1.22= 0.07 mg/L NH3. I made
my
standard according to the directions given in Standard Methods and the
conversion of 1mg/L N to 1.22 mg/L for NH3 comes from Standard
Methods.
The aquarium article does not give a toxicity value for NH3.
Phil Emmling
Environmental Chemistry & Technology Program
660 N. Park St.
Madison, WI 53706
Phone: 608 262-2899
FAX: 608 262-0454
>>> Phil Emmling <emmling@engr.wisc.edu>
7/28/2005 8:48 AM >>>
Brian,
Last night and this morning I tried my 2 kits with newly made
standards.
I made a 1000ppm N-Nh4 and diluted to 100ppm. I used the 100ppm to
make
0.5, 1.0, and 2.0 for LaMotte kit code 3304. I used the same 100ppm
standard to make 0.8 and 0.4 ppm for the low range Hach kit cube
#22669.
I made the dilute standards fresh from the 100ppm for each evening and
morning tests.
Both sets of standards gave the same but confusing results. The
LaMotte
kit has a color matching Octa slide #1100 and the standards all looked
about 1/4 of the anticipated values. Thus the 2.0, 1.0, and 0.5ppm
standards looked like 0.5, 0.25, and >0.1 or about 0.125. I repeated
the tests this morning because I thought the standards were made
incorrectly. I don't think the 1000ppm was wrong and 100ppm is a no
brainer from 1000ppm. The Hach cube read high instead of low. The
0.8ppm and 0.4ppm standards read about 1.0 and 0.6ppm respectively.
All
standards were made from the same 100ppm stock.
I called LaMotte to ask whether my LaMotte reagents are too old. I
need
to order new reagents because 2 of 3 are past recommended shelf time
(1
and 1 1/2 years). The lots were made early in 2003. The low range
Hach
cube(0,.2,.4,.6,.8) seems OK. The LaMotte kit reagent 1 is sodium
hydroxide and this is hard to rinse so I am still rinsing with 50%
sulfuric acid. I might try vinegar as a less dangerous rinse. It
seems
particularly important not to use nitrate test glassware for the
ammonia
test. The 5-10ppm nitrate levels are converted to ammonia and the
base
reagent increases carryover to the lower level ammonia test.
The Lamotte 3304 has ranges 0,.05, .1, .25, .5, 1, and 2ppm. I don't
think the 0, .05, or .1 are easy to distinguish from each other. Most
of the samples I had run at UW Stevens Point lab for ammonia/ammonium
from Castle Rock Creek in SW WI ranged around .03-.05ppm at base flow.
This creek is similar to NW Iowa springcreeks in dairy cow areas. I
think you can tell .1, .25, .5, 1, and 2ppms apart using the Octa
slide.
I need to order new reagents and try again. After I get the standards
to work, I would like to do a standard addition experiment using creek
water. Both kits use Salicylate reagents.
I think you could try these 2 kits.
Phil Emmling
Environmental Chemistry & Technology Program
660 N. Park St.
Madison, WI 53706
Phone: 608 262-2899
FAX: 608 262-0454
>>> Phil Emmling <emmling@engr.wisc.edu>
8/9/2005 2:34 PM >>>
Brian,
I received fresh reagents from LaMotte and it made a big difference.
The replacement 3 reagents cost $25.50. I think you have the kit
number. It is difficult to match the color with the Octet reader but
if
it is darker than 0.025 and lighter than 1.00, it could be reported as
0.050 or the color in the middle. I won't have time this week to play
with it using standard additions. The test takes about 25 minutes.
It
will distinguish <0.50 from 1 and 2ppm. Perhaps it works best as a
red
flag than a test for spatial or temporal trend analysis. I used
vinegar
instead of 50% sulfuric acid to clean the glassware and it seemed to
work OK. I would suggest having the Iowa DNR lab play with the
ammonia
test. If you decide on a test I would like to know which one worked.
I
would rate this test about as good as the standard N-nitrite/nitrate
test.
Phil Emmling
Environmental Chemistry & Technology Program
660 N. Park St.
Madison, WI 53706
Phone: 608 262-2899
FAX: 608 262-0454
>>> "Linda Green" <LGreen@uri.edu>
8/17/2005 2:00 PM >>>
Hi Brian,
Here at URI Watershed Watch we have our own
analytical lab and use an Astoria-Pacific segmented continuous flow
nutrient
autoanalyzer for our nutrient analyses, since our waters are typically
<2ppm
in any form of nitrogen, which I think is pushing the limit on kits. I
was
fortunate that our Dean contributed ~ 75% of the $42K it cost to
purchase
the autoanalyzer last year, it was replacing a 15 year old model that
had
been purchased by a professor I worked with. The prof departed a
number of
years ago without the analyzer, I took it over. My background is in
soils
and chemistry and I already was a lab tech when I started Watershed
Watch so
I was fortunate to have good lab access, and also great support from
URI and
my college.
Analyzing ammonium-N was pain with the old autoanlayzer, much
better
with the new one, my detection limit is ~ 20 ppb, 0.020 ppm as N.
Elizabeth Herron shared with me your reply about top 3 choices
for
NWQ 06 vol mon workshops. We really appreciate your enthusiastic
response!
Cheers!
Linda
URI Cooperative Extension Water Quality
Department of Natural Resources Science
1 Greenhouse Road
Kingston, RI 02881-0804
401-874-2905
www.uri.edu/ce/wq/
www.usawaterquality.org/volunteer
