David J. Blumer, Ph. D.

Principal Scientist
Production Assurance Technology
223 GB, BTC
Bartlesville, OK 74004
Phone 918-661-5414
Cell (907)-227-2439
David.blumer@conocophillips.com
www.conocophillips.com

Water Sampling and Analysis Specification

This document defines the "Standard Water Analysis" that specifies the complete suite of
species and some suggestions on sampling and analytical techniques. The results of this
extensive list of analyses are the required input for the various computer multi-component
simultaneous equilibrium chemistry models that can correctly predict the changes in the water
chemistry, scale precipitation, rock-water interactions, water sources and mixing, and
corrosion.

Certain measurements must be taken in the field at the sampling point coincident with taking the
sample, since these values change quickly once the sample is removed:

Table 1. Water Sampling On-site Data and Analyses

Temperature
pH
Eh (optional)
Dissolved O2 (Chemet or meter)
H2S
CO2
Pressure
Bicarbonate (HCO3-) alkalinity titration (recommended)

Sample Containers: Obtain 3 bottles for each sample that is taken: 1 for Cations/Metals, 1 for
Anions/etc., and 1 for organic acids. The bottles should be polyethylene, Teflon, or
polycarbonate.

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Table 2. Water Sampling – “Bottle A” (acidified) for Cations/Metals

Cation Species Analytical Technique Sample Treatment

Na ICP or DCP, AA Acidified with 10 ml Ultrapure HNO3
K ICP or DCP, AA In 1 liter polyethylene, Teflon, or
Li ICP or DCP, AA polycarbonate bottle.
Ca ICP or DCP, AA
Mg ICP or DCP, AA
Sr ICP or DCP, AA
Ba ICP-MS, ICP or DCP
Fe ICP or DCP, AA
Mn ICP-MS, ICP
Al ICP-MS, ICP
Cr ICP-MS, ICP
Si ICP or DCP
B ICP or DCP, ICP-MS
P ICP-MS, ICP

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 Table 3. Water Sampling – “Bottle B” (no additions) for Anions, etc.

Anion Species Analytical Technique Sample Treatment

Ion Chromatography (IC) or
-
Cl EC No additives, fill completely
Capillary Electrophoresis
-
Br (CE) or IC 1 Liter polyethylene, Teflon,
-
F Ion Selective Electrode or Polycarbonate bottle.
-
I Ion Selective Electrode
=
SO4 IC or CE
-
NO3 IC or CE
=
S Ion Selective Electrode
cation that can't be done on
+
NH 4 Ion Selective Electrode or IC "Bottle A"
should be done at sampling
-
HCO3 Titration or TOC Analyzer site, too
should be done at sampling
=
CO3 Titration site, too
Resistivity Resistivity Probe
Conductivity Conductivity cell
should be done at sampling
pH (Lab) pH meter site, too
should be done at sampling
Eh (Lab) ORP (pH) meter site, too

Table 4. Water Sampling - “Bottle C” (biocide) for Organic Acids

Organic Acids Analytical Technique Sample Treatment

Acetic IC or CE 1 ml Glutaraldehyde
Propionic IC or CE in 250 ml polyethylene, Teflon
Butyric IC or CE or polycarbonate bottle

Filter a measured portion of the sample taken for the Anion analysis through a 0.45 micron filter
to measure the Total Suspended Solids (TSS). In the case where a large amount of solids are
collected, the filter paper should be saved for later SEM/EDS analysis to determine identity of
the solids.

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It is specified that the bottles for the Cation and Organic Acids analyses have additives put in
them; 10 ml of Ultrapure nitric acid (HNO3) for the ICP analysis and 1 ml of glutaraldehyde for
the organic acids. This is to stabilize the samples so that precipitation of the metals does not ruin
the results for the ICP analysis. In particular, the iron will precipitate as the sample sits and that
precipitate removes many of the other species from solution, too. Also, we discovered that the
naturally-present bacteria in the water will quickly eat the organic acids in the samples unless we
add the biocide to that sample, so many times if no glutaraldehyde has been added, no organic
acids are detected. Therefore, adding the glutaraldehyde to bottle used for the organic acid
analysis is highly recommended.

In addition to the water analysis, the gas in contact with the water is important, too. I
recommend taking a gas sample at the same time, though one taken at a different time is usually
OK. The main things of interest in the gas are the CO 2 and H2S. The H2S analysis usually is
done at the sampling point. The CO 2 and H2S are very important in predicting what will happen
with the water.

All of this data constitutes the input to the computer programs that will then predict the stability
of the water with respect to precipitation of scales as a function of temperature and pressure.

In general, we also recommend doing bacterial surveys, primarily using serial dilution technique
using 1 media for Sulfate Reducing Bacteria (SRB) and another for media for General
Anaerobic Bacteria (GAB). Many times the exact media composition (and sometimes the
incubation temperature) has to be adjusted for a particular field to get that population to grow
well. The bacteria have a lot of negative side effects, such as generating H 2S, causing a safety &
corrosion problem and making the schmoo formation in the produced water problem worse.
Microbial induced corrosion can be very severe.