PROGRAMS AND PLANS--Guidelines for sampling and analysis of water-quality constituents associated with solids

                                           June 22, 1971

QUALITY OF WATER BRANCH TECHNICAL MEMORANDUM NO. 71.09

Subject: PROGRAMS AND PLANS--Guidelines for sampling and 
         analysis of water-quality constituents associated 
         with solids

Quality of Water Branch Technical Memorandum 71.05 described 
the largely self-evident basis for sampling and analyzing the 
suspended solids phase when investigating water-quality 
constituents that are known to be associated with suspended 
solids. Reference was made also to guidelines that would be 
provided to field offices for use in planning investigations 
that include these constituents.

At a recent meeting of the Branch staff with other Division 
water quality specialists, constituents of interest were 
classified geochemically, and recommended interim procedures 
and methods for the investigation of those constituents were 
outlined. Decisions made at this meeting reflect the 
collective knowleoge and opinion of a large cross section of 
Division research and operations personnel. They also reflect 
what is believed to be a reasonable balance between the 
desire for technical exactness and the necessity of 
practicality in field operations.

At the meeting, it was concluded that adequate data for 
making certain important decisions are not presently 
available, but possibly can be obtained within the next few 
months, in time for dissemination of final instructions to be 
effective at the beginning of the 1972 water year. Pending 
release of final instructions, the following interim 
instructions are provided as a basis for conducting 
investigations of the elements of interest.

I. Classification of minor elements or compounds associated 
   with solids:

A. Organics, pesticides

B. Organics, all others

C. Nitrogen and phosphorus

D. Inorganic anions

   1. Weakly sorbed--selenium (Se), tellurium (Te), boron 
      (B), halogens (Br, I, F).

   2. Moderately sorbed--molybdenum (Mo), vanaclium (V), 
     chromium (Cr), arsenic (As), uranium (U).

E. Inorganic cations

   1. Moderately sorbed--lithium (Li), radium (Ra), strontium 
      (Sr).

   2. Strongly sorbed--cesium (Cs), rubidium (Rb), iron (Fe), 
      manganese (Mn), copper (Cu), lead (Pb), zinc (Zn), 
      cadmium (Cd) cobalt (Co), mercury (Hg), silver (Ag), 
      gold (Au), aluminum (Al), nickel (Ni), beryllium (Be).

II. Types of investigations:

A. Reconnaissance--short one-time evaluation; can provide 
definition of problems.

B. Monitoring--repetitive, continuing measurements; can 
define variations and trends.

C. General resource appraisal--a moderately long-term 
monitoring program, but with a defined duration; typical of 
many WRD basin studies .

D. Detailed study, topical or areal--an intensive 
investigation of limited duration.

III. Phases which should be studied in WRD investigations:

Minor elements or compounds in water can occur in two 
phases--dissolved, and associated with solids. The solids 
can, of course, be suspended or on the bed. The phases to be 
investigated for each of the classes of minor elements or 
compounds and for each type of investigation are listed 
below:

A. Dissolved or sorbed on suspended solids:

1. Reconnaissance 
   a. Inorganic cations and anions--study both the material
in solution and the material sorbed on suspended solids 
   b. Nitrogen and phosphorus--study both phases 
   c. Organics--
      Dissolved organic carbon (DOC)--study only the
         dissolved phase
      Suspended organic carbon and all other organics--study 
        both phases.

2. Monitoring--same as reconnaissance.

3. General resource appraisal--same as reconnaissance.

4. Detailed study--same as reconnaissance.

B. Sorbed on bottom material:

Bottom material, especially the fine fraction, serves as an 
integrator of chemical and biological processes that occur in 
the stream, and commonly is a useful indicator of the nature 
of the solids that will be carried by the stream during the 
early stages of the next significant runoff event. Thus, it 
should be sampled at lease once at any study site, especially 
if samples of suspended material cannot be obtained during 
the early stages of runoff events, Because a new supply of 
fine material is deposited after each runoff event, a 
reasonable period of time is required to allow the 
integration process to take place before sampling. Prediction 
of the quantity of an element transported with the bedload on 
the basis of the size distribution of bed-material samples is 
questionable at present.

1. Reconnaissance--at least one sample of bed material should 
be collected in the reach studied if suspended-solids samples 
are not obtained during the early part of a stream rise.

2.  Monitoring--bed-material samples not required if 
suspended solids are adequately sampled; otherwise take at 
least one sample.

3. General resource appraisal--sample bed material.

4. Detailed study--sample bed material.

IV. Analytical techniques:

A. Size of filter pore opening--for the present, continue to 
use 0. 45 um pore size for separating dissolved (liquid) 
phase from solids phase.

B. When to filter a sample--filtering immediately after 
collection is recommended. Samples must be filtered within 
24 hours after collection.

C. Recoverable (partial extraction) vs. total destruction--
measurement of the recoverable portion of inorganic 
constituents is highly recommended. See attached procedure 
for a description of the analytical technique currently 
favored to extract and measure the recoverable fraction. 
Extraction techniques for bed material samples will be 
provided at a later date.

D. Type of filter to be used for separation of dissolved 
phase from solids phases, and type of sample used for 
analysis of solids phase:


Constituents to        Filter         To leach from solids,
be determined          type           extract from
___________________________________________________________
Organics-carbon       Silver 1/       whole-water sample 1/
Organics-all others   Silver          whole-water sample
Nitrogen & Phosphorus Membrane        whole-water sample
Inorganic anions      Membrane 1/     whole-water sample 1/
Inorganic cations     Membrane 1/     whole-water sample 1/
___________________________________________________________

1/ Whole-water sample to be used at least through 1971 water 
year. Extraction techniques for analyzing material retained 
on the filter pad will be developed and tested. After 
comparison with whole-water extraction, decision may be 
revised. A whole-water sample is defined as a representative 
sample of the water-suspended solids mixture in the cross 
section of a flowing stream, or in a vertical (or portion of 
a vertical) of a lake or reservoir. Content of constituent in 
solids phase must be calculated by difference (content in 
whole-water sample minus content in dissolved phase).

E. A separate sample will be required for determination of 
the concentration of suspended solids in the whole-water 
sample.

F. The extraction procedures for recoverable inorganic 
constituents (attached) is applicable to all minor-element 
inorganic anions and cations that are listed under I., D and 
E, above. Extraction procedures for pesticides and nutrients 
(nitrogen and phosphorus) are already in use.

V. Sampling

A.  Generally, sorption capacity per unit weight of solids 
decreases with increasing particle size. However, due to 
coatings on coarse grains (coarser than about 0. 5 mm) and 
aggregation of fine material, the content of the constituents 
of interest in the coarser size fractions cannot be ignored; 
the only exception might be in the analysis of bed-material 
samples for reconnaissance studies (see V., B).

B. For reconnaissance bed-material sample, analyze only 
material finer than 20 ,um (except for organic analysis, 
separate in field by timed multiple decantations--
instructions will be provided upon request). Samples for 
organic analysis should not be separated in the field.

C. For special purposes, sample benthic organisms and analyze 
for minor-element content.

D. If only the dissolved phase is to be determined and 
reported, sediment-sampling equipment may not be required. 
Nevertheless, the sample should be representative of the 
entire stream cross section or lake vertical. Established 
chemical-quality sampling procedures should be used.

E. When sampling for the suspended-solids phase (whole-water 
sample), sediment sampling techniques must be used. 
Procedures outlined in Interagency Committee on Water 
Resources, Subcommittee on Sedimentation Report 14, and TWRI 
Book 3, Chapter C2, Field Methods for Measurement of Fluvial 
Sediment, must be followed.

F. Teflon nozzles for sediment samplers are mandatory when 
collecting samples for the determination of inorganic minor 
elements, and are acceptable when sampling for the 
determination of organic constituents. Nozzles will be 
supplied by this office upon request. We have nozzles for the 
D-48, DH-59, D-49, and P-61 samplers.

G. The black rubber gasket in sediment samplers must be 
replaced with a silicone-rubber gasket when collecting 
samples for the determination of minor elements and organics. 
Silicone-rubber gaskets for the samplers listed above will be 
supplied by this office upon request.

H. One liter is the minimum sample volume required for the 
determination of minor elements associated with suspended 
solids.

I. Presently used pint milk bottles are satisfactory for the 
interim for collecting whole-water samples, but the samples 
should be quantitatively transferred in the field (except 
when sampling for organics) to an approved screw-top bottle. 
Samples collected for organic determinations should receive a 
minimum amount of handling in the field.

J. A handscoop made from a cut-out plastic bottle or other 
straightsided plastic container may be used for 
reconnaissance sampling of bottom sediments when the stream 
can be waded. Samples collected should be iced in the field. 
When sampling bottom sediments with the BM-54 and BMH-60 bed-
material samplers, the buckets on the samplers must be 
thoroughly cleaned before each use, and the rubber gaskets 
must be replaced by silicone rubber gaskets. Requests for 
these gaskets should be made through this office.

K. The valve mechanism in the P-61 and 63 point samplers may 
pose a serious contamination problem. Use of point samplers 
for sampling minor elements should be avoided unless notifed 
otherwise .

The above instructions indicate, in effect, that if a 
quantitative analysis of constituents associated with 
suspended solids is to be made, it must be made using a 
sample that is representative of both the suspended solids 
and the liquid phase in the cross section sampled. If the 
required sampling effort cannot be justified, it is better to 
filter the sample and analyze for the dissolved constituents 
only.

The Quality of Water Branch will be interested in receiving 
written comments from the field pertaining to the interim 
guidelines given above. Further guidelines will be 
forthcoming.



                                  W. H. Durum

Attachment

WRD Distribution A, B, S, FO, PO.