A BRIEF GUIDE TO THE PRESERVATION OF

WASTEWATER SAMPLES

Deshai Botheju

28.09.2007 A Brief Guide to the Preservation of Wastewater Samples - Deshai

Aims of wastewater sample Preservation

1. Retard biological actions

2. Retard hydrolysis & other Reactions of chemical compounds
3. Reduce the volatility of components

Preservation Methods
Limited basically to,
1. Chemical addition
2. pH control
3. Refrigeration (in liquid state)
4. Freezing

Chemical addition: chemical addition to preserve for one parameter can lead to interfere
with other parameters, then additional sampling must be done for them.

pH control: usually involves acid addition to lower ph<2

Refregeration
- also includes the icing in field works
- very common
- no effect on sample composition
- does not maintain integrity for all parameters for a long time

Freezing ??
- argumental
- equilibrium of different particle size ranges can be dramatically changed
- vigorous homogenization (e.g. ultrasonic homogenization) is required before
analysis at least to minimize the above effect
- soluble components can also be changed due to particle/cell splitting
- only acceptable for certain analysis
- not acceptable as a general preservation scheme

28.09.2007 A Brief Guide to the Preservation of Wastewater Samples - Deshai

Sample size
-Depends on the purpose
-At least 100 ml to minimize solid bias
-Sample volume must be large enough to keep an extra
amount for quality control after finishing all the analyses

Analysis Holding Time

SOONER THE BETTER!

-Shorter the time period between sampling and

analysis, the more reliable will be the analytical
results
-Complete preservation is IMPOSSIBLE !
-Note that biological actions involving N and P are
the most notorious on changing samples

Suggested Methods for selected Parameters

General Parameters
Parameter Container Preservative Max.
material method Holding time
Alkalinity PE, GL Cool 4 oC 14 d
Ammonia PE, GL H2SO4 pH<2 28 d
Cool 4oC
COD PE, GL H2SO4 pH<2 28 d
Cool 4oC
pH PE, GL - immediate
Organic carbon PE, GL HCL/H2SO4 pH<2 28 d
Cool 4oC

28.09.2007 A Brief Guide to the Preservation of Wastewater Samples - Deshai

P - elemental GL Cool 4oC 48 hr
P -total PE, GL H2SO4 pH<2 28 d
Cool 4oC
Sulfate PE, GL Cool 4oC 28 d
Sulfide PE, GL see note 1 7d
Sulfite PE, GL Cool 4oC immediate

Solids
Parameter Container Preservative Max.
material method Holding time
TS PE, GL Cool 4oC 7d
Filterable solids PE, GL Cool 4oC 7d
TSS PE, GL Cool 4oC 7d
Settlable solids PE, GL Cool 4oC 48 hr
VS PE, GL Cool 4oC 7d
Turbidity PE, GL Cool 4oC 48 hr

Different N compounds
Parameter Container type Preservation Maximum Holding
method time
Ammonia Glass, Plastics (PE) Cool 4oC and add 28 d
H2SO4 pH < 2
Kjeldahl and Glass, Plastics (PE) Cool 4oC and add 28 d
Organic N H2SO4 pH < 2
Nitrate + nitrite Glass, Plastics (PE) Cool 4oC and add 28 d
H2SO4 pH < 2
Nitrate Glass, Plastics (PE) Cool 4oC 48 hr
Nitrite Glass, Plastics (PE) Cool 4oC 48 hr
Acrylonitrile Glass + Teflon Cool 4oC and add 14 d
Lined cap 0.008% Na2S2O3
Nitrosamines Glass + Teflon lined Cool 4oC and add 7 days until
cap 0.008% Na2S2O3, extraction, 40 days
store in dark after extraction
Nitroaromatics Glass + Teflon lined Cool 4oC 7 days until
cap extraction, 40 days
after extraction

Abbreaviations: Ref – Refrigeration; d – days; hr – hours; PE-polyethylene; GL-glass

28.09.2007 A Brief Guide to the Preservation of Wastewater Samples - Deshai

Sampling container
PE-Polyethylene
Other plastic types suitable : polypropylene,
polycarbonate, rigid polyvinyl chloride, Teflon
GL- glass
Klimax or Pyrex brand borosilicate glass are suitable

Container caps
Polyethylene or Bakelite caps with liners are suitable
Teflon caps are better, but expensive

Wide mouth containers are more suitable in most of the cases

General cleaning procedure for sample containers

-Wash containers and caps with a non-phosphate detergent and scrub strongly with a
brush
- If possible separate bottle caps and their liners and wash separately
- Rinse first with tap water and then with distilled water.
-Invert to drain and dry

While sampling and Transporting the sample

- Ensure representiveness of the sample ! The sample must truly represent the
existing conditions
- Temperature and ph must be tested on site
- Add preservatives (if using) to the bottle before pouring the sample
- As a rule of thumb for field, 2 ml (2 drops) of H2SO4 (concentrated) per one litre
of sample may bring the ph below 2.0
- Close the container cap tightly just after sampling
- Tag or lable the each sample with clarity - include the date, time, collectors name,
location/point, and any other detail specifically necessary
- Icing can reliably use as a temporary preservation mean while transporting
samples to the lab

28.09.2007 A Brief Guide to the Preservation of Wastewater Samples - Deshai

Cautions !
-Depending on the source some samples may not be stable for
the whole time period indicated in the above table

-Only after proving the stability, some regular samples from the
same source may be held for longer durations

-Samples without pH adjustments (for those parameters that the

table recommends pH adjustments) must be analyzed within 7
days.
-Special cleaning and container preparation procedures must be
followed for some parameters.

28.09.2007 A Brief Guide to the Preservation of Wastewater Samples - Deshai