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Ref. No. [UMCES] CBL 2015-014

ACT VS15-07

3

EXECUTIVE SUMMARY

The Alliance for Coastal Technology (ACT) conducted a sensor verification study of in

situ pH sensors during 2013 and 2014 to characterize performance measures of accuracy and

reliability in a series of controlled laboratory studies and field mooring tests in diverse coastal

environments. A ten week long laboratory study was conducted at the Hawaii Institute of

Marine Biology and involved week long exposures at a full range of temperature and salinity

conditions. Tests were conducted at three fixed salinity levels (0.03, 22, 35) at each of three

fixed temperatures (10, 20, 30

o

C). Ambient pH in the test tank was allowed to vary naturally

over the first five days. On the sixth day the pH was rapidly modified using acid/base additions

to compare accuracy over an extended range and during rapid changes. On the seventh day the

temperature was rapidly shifted to the next test condition. On the tenth week a repeated seawater

trial was conducted for two days while the temperature was varied slowly over the 10 – 30

o

C

range. Four field-mooring tests were conducted to examine the ability of test instruments to

consistently track natural changes in pH over extended deployments of 4-8 weeks. Deployments

were conducted at: Moss Landing Harbor, CA; Kaneohe Bay, HI; Chesapeake Bay, MD; and

Lake Michigan, MI. Instrument performance was evaluated against reference samples collected

and analyzed on site by ACT staff using the spectrophotometric dye technique following the

methods of Yao and Byrne (2001) and Liu et al. (2011). A total of 263 reference samples were

collected during the laboratory tests and between 84 – 107 reference samples were collected for

each mooring test. This document presents the results of the Xylem EXO 2 pH sensor which

measures pH using a glass bulb electrode and KCl reference electrode. For most tests two pH

sensors were included on the sonde and results are presented separately for each.

The EXO-pH1 operated continuously throughout the entire lab test and generated 6286

pH measurements at 15 minute intervals. The total range of pH measured by the EXO-pH1 was

7.04 to 8.50, compared to the range of our reference pH of 6.943 to 8.502. The EXO-pH1

measurements tracked changing pH conditions among all water sources and temperature ranges,

and consistently responded to the rapid pH shifts from acid/base additions. The average

difference between the EXO-pH1 and reference pH was 0.05 ±0.09 (N=266), with a total range

of -0.31 to 0.19. Initial instrument measurements conducted with the second seawater trial on

the tenth week exhibited a slightly higher offset (mean difference = 0.17 ±0.004; N=7) compared

to measurements from the first week (mean difference = 0.10 ± 0.004; N=28)

The EXO-pH2 also operated continuously throughout the entire lab test and generated

6286 pH measurements at 15 minute intervals. The total range of pH measured by the EXO-pH2

was nearly identical at 7.03 to 8.49, and again in close agreement with the range of the reference

pH of 6.943 to 8.502. The EXO-pH2 measurements tracked reference pH similarly among all

water sources and temperature ranges, and consistently responded to the rapid pH shifts from

acid/base additions. The average difference between the EXO-pH2 and reference pH was 0.04

±0.10 (N=266), with a total range of -0.31 to 0.19. Initial instrument measurements conducted

with the second seawater trial on the tenth week exhibited a slightly higher offset (mean

difference = 0.17 ±0.003; N=7) compared to measurements from the first week (mean difference

= 0.08 ± 0.007; N=28)

At Moss Landing Harbor the field deployment test was conducted over 28 days with a

mean temperature and salinity of 16.6

o

C and 33. The measured ambient pH range from our 84

discrete reference samples was 7.933 – 8.077. The EXO sonde deployed for this field test

contained two pH probes and both operated continuously over the 28 days of the deployment and