Can we be sure that fun in the sun alters water chemistry?

Minimalist sampling and experimental variables


Keith S. Taber


Dirty water

I was reading the latest edition of Education in Chemistry and came across an article entitled "Fun in the sun alters water chemistry. How swimming and tubing are linked to concerning rises in water contaminants" (Notman, 2023). This was not an article about teaching, but a report of some recent chemistry research summarised for teachers. [Teaching materials relating to this article can be downloaded from the RSC website.]

I have to admit to not having understood what 'tubing' was (I plead 'age') apart from its everyday sense of referring collectively to tubes, such as those that connect Bunsen burners to gas supplies, and was intrigued by what kinds of tubes were contaminating the water.

The research basically reported on the presence of higher levels of contaminants in the same body of water at Clear Creak, Colorado on a public holiday when many people used the water for recreational pursuits (perhaps even for 'tubing'?) than on a more typical day.

This seems logical enough: more people in the water; more opportunities for various substances to enter the water from them. I have my own special chemical sensor which supports this finding. I go swimming in the local hotel pool, and even though people are supposed to shower before entering the pool: not everyone does (or at least, not effectively). Sometimes one can 'taste' 1 the change when someone gets in the water without washing off perfume or scented soap residue. Indeed, occasionally the water 'tastes' 1 differently after people enter the pool area wearing strong perfume, even if they do not use the pool and come into direct contact with the water!

The scientists reported finding various substances they assumed were being excreted 2 by the people using the water – substances such as antihistamines and cocaine – as well as indicators of various sunscreens and cosmetics. (They also found higher levels of "microbes associated with humans", although this was not reported in Education in Chemistry.)


I'm not sure why I bother having a shower BEFORE I go for a swim in there… (Image by sandid from Pixabay)


It makes sense – but is there a convincing case?

Now this all seems very reasonable, as the results fit into a narrative that seems theoretically feasible: a large number of people entering the fresh water of Clear Creek are likely to pollute it sufficiently (if not to rename it Turbid Creek) for detection with the advanced analytical tools available to the modern chemist (including "an inductively coupled plasma mass spectrometer and a liquid chromatography high resolution mass spectrometer").

However, reading on, I was surprised to learn that the sampling in this study was decidedly dodgy.

"The scientists collected water samples during a busy US public holiday in September 2022 and on a quiet weekday afterwards."

I am not sure how this (natural) experiment would rate as a design for a school science investigation. I would certainly have been very critical if any educational research study I had been asked to evaluate relied on sampling like this. Even if large numbers of samples were taken from various places in the water over an extended period during these two days this procedure has a major flaw. This is because the level of control of other possibly relevant factors is minimal.

Read about control in experimental research

The independent variable is whether the samples were collected on a public holiday when there was much use of the water for leisure, or on a day with much less leisure use. The dependent variables measured were levels of substances in the water that would not be considered part of the pristine natural composition of river water. A reasonable hypothesis is that there would be more contamination when more people were using the water, and that was exactly what was found. But is this enough to draw any strong conclusions?

Considering the counterfactual

A useful test is to ask whether we would have been convinced that people do not contaminate the water had the analysis shown there was no significant difference in water samples on the two days? That is to examine a 'counterfactual' situation (one that is not the case, but might have been).

In this counterfactual scenario, would similar levels of detected contaminants be enough to convince us the hypotheses was misguided – or might we look to see if there was some other factor which might explain this unexpected (given how reasonable the hypothesis seems) result and rescue our hypothesis?

Had pollutant levels been equally high on both days, might we have sought ('ad hoc') to explain that through other factors:

  • Maybe it was sunnier on the second day with high U.V. levels which led to more breakdown of organic debris in the river?
  • Perhaps there was a spill of material up-river 3 which masked any effect of the swimmers (and, er, tubers?)
  • Perhaps rainfall between the two sampling dates had increased the flow of the river and raised its level, washing more material into the water?
  • Perhaps the wind direction was different and material was being blown in from nearby agricultural land on the second day.
  • Perhaps the water temperature was different?
  • Perhaps a local industry owner tends to illegally discharge waste into the river when the plant is operating on normal working days?
  • Perhaps spawning season had just started for some species, or some species was emerging from a larval state on the river bed and disturbing the debris on the bottom?
  • Perhaps passing migratory birds were taking the opportunity to land in the water for some respite, and washing off parasites as well as dust.
  • Perhaps a beaver's dam had burst up stream 3 ?
  • Perhaps (for any panspermia fans among readers) an asteroid covered with organic residues had landed in the river?
  • Or…

But: if we might consider some of those factors to potentially explain a lack of effect we were expecting, then we should equally consider them as possible alternative causes for an effect we predicted.

  • Maybe it was sunnier on the first day with high U.V. levels which led to more breakdown of organic debris in the river?
  • Perhaps a local industry owner tends to illegally discharge waste into the river on public holidays because the work force are off site and there will be no one to report this?
  • … etc.

Lack of control of confounding variables

Now, in environmental research, as in research into teaching, we cannot control conditions in the way we can in a laboratory. We cannot ensure the temperature and wind direction and biota activity in a river is the same. Indeed, one thing about any natural environment that we can be fairly sure of is that biological activity (and so the substances released by such activity) varies seasonally, and according to changing weather conditions, and in different ways for different species.

So, as in educational research, there are often potentially confounding variables which can undermine our experiments:

In quasi-experiments or natural experiments, a more complex design than simply comparing outcome measures is needed. …this means identifying and measuring any relevant variables. …Often…there are other variables which it is recognised could have an effect, other than the dependent variable: 'confounding' variables.

Taber, 2019, p.85 [Download this article]

independent variableclass of day (busy holiday versus quiet working day)
dependent variablesconcentrations of substances and organisms considered to indicate contamination
confounding variablesanything that might feasibly influence the level of concentrations of substances and organisms considered to indicate contamination – other than the class of day
In a controlled experiment any potential confounding variables are held at fixed levels, but in 'natural experiments' this is not possible

Read about confounding variables in research

Sufficient sampling?

The best we can do to mitigate for the lack of control is rigorous sampling. If water samples from a range of days when there was high level of leisure activity, and a range of days when there was low level of leisure activity were compared, this would be more convincing that just one day from each category. Especially so if these were randomly selected days. It is still possible that factors such as wind direction and water temperature could bias findings, but it becomes less likely – and with random sampling of days it is possible to estimate how likely such chance factors are to have an effect. Then we can at least apply models that suggest whether observed differences in outcomes exceed the level likely due to chance effects.

Read about sampling in research

I would like to think that any educational study that had this limitation would be questioned in peer review. The Education in Chemistry article cited the original research, although I could not immediately find this. The work does not seem to have been published in a research journal (at least, not yet) but was presented at a conference, and is discussed in a video published by the American Chemical Society on YouTube.

"With Labor Day approaching, many people are preparing to go tubing and swimming at local streams and rivers. These delightful summertime activities seem innocuous, but do they have an impact on these waterways? Today, scientists report preliminary [sic] results from the first holistic study of this question 4, which shows that recreation can alter the chemical and microbial fingerprint of streams, but the environmental and health ramifications are not yet known."

American Chemical Society Meeting Newsroom, 2023

In the video, Noor Hamdan, of John Hopkins University, reports that "we are thinking of collecting more samples and doing some more statistical analysis to really, really make sure that humans are significantly impacting a stream".

This seems very wise, as it is only too easy to be satisfied with very limited data when it seems to fit with your expectations. Indeed that is one of the everyday ways of thinking that science challenges by requiring more rigorous levels of argument and evidence. In the meantime, Noor Hamdan suggests people using the water should use mineral-based rather than organic-based sunscreens, and she "recommend[s] not peeing in rivers". No, I am fairly sure 'tubing' is not meant as a euphemism for that. 5


Work cited:

Notes:


1 Perhaps more correctly, smell, though it is perceived as tasting – most of the flavour we taste in food is due to volatile substances evaporating in the mouth cavity and diffusing to be detected in the nose lining.


2 The largest organ of excretion for humans is the skin. The main mechanism for excreting the detected contaminating substances into the water (if perhaps not the only pertinent one, according to the researchers) was sweating. Physical exertion (such as swimming) tends to be associated with higher levels of sweating. We do not notice ourselves sweating when the sweat evaporates as fast as it is released – nor, of course, when we are immersed in water.


One of those irregular verbs?

I perspire.

You sweat.

She excretes through her skin

(Image by Sugar from Pixabay)


3 The video suggests that sampling took place both upriver and downriver of the Creek which would offer some level of control for the effect of completely independent influxes into the water – unless they occurred between the sampling points.


4 There seem to be plenty of studies of the effects of water quality on leisure use of waterways: but not on the effects of the recreational use of waterways on their quality.


5 Just in case any readers were also ignorant about this, it apparently refers to using tyre inner tubes (or similar) as floatation devices. This suggests a new line of research. People who float around in inner tubes will tend to sweat less than those actively swimming – but are potentially harmful substances leached from the inner tubes themselves?


Join an email discussion list for those teaching chemistry