Case study 5: Benzotriazoles - emerging contaminants in lakes?

Introduction

Benzotriazole (BT) and tolytriazole (TT) represent some of the emerging contaminants in
aquatic systems. They are widely used as anticorrosive additives, e.g., in cooling and hy-
draulic fluids, in antifreezing products, in aircraft deicer and antiicer fluid (ADAF), and in
dishwasher detergents for silver protection1.

H H
N N
N N
N N
Scheme 1: Benzotriazole and tolytriazole

Owing to their polarity and thus high water solubility and low octanol-water partitioning
behavior, they have been found in considerable concentrations in Swiss rivers corresponding
to weekly loads of several kg. Because of their application as household detergent additives,
these chemicals are very widely used as so-called down-the-drain chemicals, which are dis-
charged in municipal wastewaters and persist in natural waters.

Exercise

Your task is to investigate the fate of benzotriazole and tolytriazole in Greifensee to obtain an
overview of its elimination processes. Note that to date, only few studies have tried to quan-
tify the inputs of these compounds in lakes.

(a) Using MatLab, design a model for the annual concentration time courses of benzotri-
azole and tolytriazole in Greifensee and compare the results to measured concentrations
published by Giger et al.1.

(b) Even though benzotriazole and tolytriazole have been found to resist biodegradation
you expect a contribution of photolysis to the elimination of these compounds in lakes. Esti-
mate the contribution of photochemical transformation to the overall elimination in Greifen-
see. Use measured data to calibrate your model.

Substance and system data

Substance data on BT and TT including concentration measurements in Greifensee and

properties of Greifensee can be found in references 1,2. Access to pdf-versions of cited papers
or single chapters from Environmental Organic Chemistry is provided via the course webpage,
ISI web of science, or via the publishers of the textbook (Wiley, you need to access the web
within the ETHZ domain: http://www3.interscience.wiley.com/search/allsearch; search
'onlinebooks' for Environmental Organic Chemistry).

Presentation & report

In the presentation of your results, introduce the sources and sinks of benzotriazole and toly-
triazole and how they affect their concentration in Greifensee. Which parameters are the
most sensitive ones for an accurate simulation? Note that your colleagues are familiar with
the modeling procedures but do not necessarily know the environmental chemistry of ben-
zotriazole and tolytriazole. Presentations should last 10 to 15 minutes so that 5-10 minutes
are left for questions and a discussion.
Use the feedback obtained from these discussions to compose a short report (max. 5 pages),
which should contain (1) a short introduction of the processes affecting the fate of the con-
taminants in lakes, (2) a complete list of the parameters use for the concentration modeling,
(3) a description of the simulation outcome, and (4) a discussion of the results and, option-
ally, issues encountered during concentration modeling.

Deadlines
Presentation: April 24, 20007

Written report: April 30, 2007; to be submitted electronically to one of the tutors.

Assistance
For assistance with the exercise, substance or lake properties as well as for problems associ-
ated with the use of MatLab ask one of the tutors either Tuesdays from 10-12 am or via e-
mail.

Literature

(1) Giger, W.; Schaffner, C.; Kohler, H. P. E. Benzotriazole and tolyltriazole as aquatic con-
taminants. 1. Input and occurrence in rivers and lakes; Environ. Sci. Technol. 2006, 40 (23),
7186-7192.

(2) Schwarzenbach, R. P.; Gschwend, P. M.; Imboden, D. M. Environmental Organic Chem-

istry; 2nd ed.; John Wiley & Sons: New York, 2003.