Page 14 - Shimadzu Journal vol.7 Issue1

Environmental Analysis

How new collaborations improve environmental results

William Lipps, Chief Science Officer, Eurofins Eaton Analytical

We are collaborating with consensus standards organizations and as the Shimadzu TOC-L pictured in Fig. 1.
using Shimadzu instrumentation to create new methods that will There were a total of seven matrices tested, four of which were prepared as
improve environmental monitoring by enabling users to get data Youden pairs making a total of twelve samples to be analyzed at each
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faster, and more accurately. In the United States, environmental laboratory. In addition, each of these unknowns was prepared as blind
methods must be approved by the United States Environmental duplicates for a total of 24 vials sent as unknown to each laboratory. (See
Protection Agency (USEPA) prior to use for compliance monitoring. table 1). The matrices varied in total dissolved solids (TDS) from reagent water
The USEPA has several pathways for the generation of new methods: to seawater. In addition, the Total Organic Carbon (TOC) source material was
varied by matrix. Humic acids were added to the surface water and seawater.
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1) EPA writes their own method Primary standards ammonium, p-toluene sulfonate, glycine p-toluene
2) A company writes a new method through the Alternative Test sulfonate and nicotinic acid p-toluene sulfonate were added to groundwater,
Procedure (ATP) Process synthetic surface water, and synthetic wastewater, respectively. These
3) Use a voluntary consensus standard body (VCSB) method primary standards were used in a previous total nitrogen study (see ASTM
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D8083 below) and repeated in this study so that users could prepare known
Private companies, such as Shimadzu, have only options 1 and 2 above matrices if they so chose. Humic acids were obtained from the International
available to them. Option 2, the ATP process, is only applicable to existing Humic Substances Society . 6
regulated parameters. This procedure compares data from an existing
method to a new, or modified, method to determine if the results are
essentially the same. If so, the EPA issues a letter and may later approve the
method through the regulatory process.
Option 3, using a VCSB such as ASTM International or Standard Methods
for the Examination of Water and Wastewater, is the only way a private
company, such as Shimadzu, can get a new method, for new unregulated
parameters or using a new technique, approved by EPA. Important to note,
just because an ASTM standard or Standard Methods method is developed
does not mean EPA will approve it. However, EPA only approves methods,
not techniques, for water testing; if you want a new technique approved,
you must first have a method. In addition, we believe that once a new
consensus method is developed it has improved environmental monitoring
globally, regardless of whether the USEPA eventually approves it. Fig. 1 TOC-L
In this article, we discuss several new methods we have developed or are
developing in collaboration with Shimadzu and validating through
Table 1 Matrices used for TOC ILS
consensus organizations.

ASTM D7573 Standard Test Method for Total Carbon and
Organic Carbon in Water by High Temperature Catalytic
Combustion and Infrared Detection 1

This method was written by this author and is already published and
approved by the USEPA for wastewater reporting, however, it did not contain
ASTM required multiple-laboratory validation data. Shimadzu undertook the
necessary steps to ensure the method was validated and not removed from
the books by ASTM. In addition, we collaborated with Standard Methods
since this ASTM Standard is essentially the same as Standard Method 5310B.
There are essentially two objectives one can take when carrying out an
inter-laboratory study: (1) to compare the performances of participating
laboratories; and (2) quantitatively evaluate the reproducibility of the
analytical process. When conducting these studies at ASTM and Standard
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Methods the intent is always to determine the reproducibility of the method
(number 2) and not evaluate performance between labs. Reproducibility is a A finished tap water was spiked with KHP along with a high and low
measure of how well a method performs with different operators, different concentration in reagent water. These high and low concentrations
reagents, different instruments, at different locations. were included to evaluate the performance of the method at the
Since TOC by combustion – IR is already in use globally, we did not require calibration extremities without any potential matrix effects. The results
laboratories initially qualify. Instead, we sent samples to every laboratory that of the Youden pair samples, statistically evaluated in accordance with
volunteered. The entire ASTM D19 on water and the Standard Methods part ASTM D2777 , are shown in Table 2. Unfortunately, matrices 6 & 7
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5000 members were sent invitations to participate. Of these, we only concentrations were too low for use as Youden pairs, or were
received about 10 responses, for a total of eight labs that finally participated. accidentally spiked at similar concentrations. These matrices were
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These labs included four municipalities, two commercial testing labs, and two processed according to ASTM E691 with the non Youden pairs
instrument vendors. The laboratories used combustion-IR TOC analyzers, such shown in Table 3.

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