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8 Chemicals
Chemical hazards can enter surface waters or be deposited on beaches from anthropogenic sources or natural
sources (e.g. hyperalkaline lakes). Contamination may be from point sources, such as industrial outfalls, or
non-point (diffuse) sources, such as runoff from land. In most cases, particularly where there are riverine flows
or tidal movement, contaminants will be significantly diluted or dispersed, minimizing public health risks. There
are very few reports of human health impacts associated with recreational exposure to chemicals in fresh or
marine waters.

Chemicals may also degrade the aesthetic quality of recreational water environments, as discussed in Chapter 9.
Toxins from cyanobacteria are addressed in Chapter 5.

8.1 System assessment

8.1.1 Exposure assessment
The frequency, extent and likelihood of exposure are important inputs into assessing the risks from chemicals in
recreational waters. The form and frequency of recreational activity (7–8 swimming events per year in temperate
climates and up to 150 swimming events per year in warmer climates; Schets, Schijven & de Roda Husman,
2011; NHMRC, 2019) will therefore play a significant role. Routes of exposure can include contact with the
skin (dermal), eyes and mucous membranes; inhalation; and ingestion.

Many substances of potential concern have low water solubility and will tend to migrate to sediments, where
they may accumulate. Skin exposure may occur if the sediments are disturbed and resuspended, or where
recreational water users are in direct contact with sediments. Although little evidence is available, this type of
exposure is considered to make only a minor contribution to overall exposure.

Dermal exposure
Skin and eye irritation result from exposure to some chemicals, including cyanobacterial toxins such as
lyngbyatoxin-a (refer to Chapter 5), and alkaline and acidic substances with extreme pH (<4 or >11). Generally,
irritation will be transient and resolved by washing in clean water. Causal agents are typically not identified
except in the presence of harmful algal/cyanobacterial blooms (Chapter 5) or specific circumstances such as
swimming in unsuitable water bodies (e.g. abandoned quarry or mine pits filled with water).

Potential health impacts from most substances depend on dermal absorption (refer to USEPA, 2004; ATSDR,
2005; enHealth, 2012). Skin is an effective barrier for many chemicals; its permeability is influenced by physical
properties of the chemical. Chemicals with high permeability are typically organic chemicals of low molecular
weight that are non-ionized and lipid soluble (e.g. xylene, benzene, toluene). Exposure may be exacerbated
by broken or damaged skin. Dermal exposure may need to be considered if concentrations nearing guideline
values, based on ingestion (refer to section 8.1.1.2), are reached for chemicals with moderate to high skin
permeability. Generally, these chemicals will only be present in significant concentrations in the event of a spill.
The use of wetsuits (e.g. by windsurfers, surfers, divers) can trap water inside the suit, producing a micro-
environment that could potentially increase the risk of skin irritation and the absorption of chemicals through
the skin (see also Chapter 5).
122 GUIDELINES ON RECREATIONAL WATER QUALITY — Volume 1: coastal and fresh waters

Ingestion
Limited data are available on volumes of water ingested during recreational activities. Estimates of volumes
ingested per swimming event (95th percentiles) are 170–179 mL in children and 87–210 mL in adults in fresh
waters, and 140–250 mL in children and 124–170 mL in adults in marine waters (Schets, Schijven & de Roda
Husman, 2011; DeFlorio-Barker et al., 2017).

However, most hazardous chemicals cause harm following chronic exposure for many years. For example, most
of the chemical guideline values in the World Health Organization Guidelines for drinking-water quality (GDWQ)
are based on ingestion of 2 L per day over many years (WHO, 2017). Based on worst-case ingestion levels
per swimming event of 250 mL (children) and 210 mL (adults), and estimated frequencies of eight events per
year in temperate waters and 150 events in warmer waters, the volume of water ingested through recreational
activities would be 2 L (children) and 1.7 L (adults) per year in temperate waters, and 38 L (children) and 32
L (adults) per year in warmer waters.

Inhalation
Inhalation can be important where there is a significant amount of spray, such as during waterskiing or whitewater
canoeing. Inhalation can be of greater significance in swimming pools and related environments where chemical
disinfection is practised (WHO, 2006).

8.1.2 Chemical hazards

Potential sources of chemical hazards include:
• onshore and offshore industrial discharges and spills
• wastewater discharges
• discharges from contaminated sites
• local use of motorized crafts
• petroleum receiving stations
• pesticides
• mining wastes
• naturally occurring chemicals, including algal toxins.

Information on past industry in the recreational water catchment area will give an indication of whether
contaminated sediments are likely to be present and the identity of possible contaminants.

For recreational water users, risks associated with chemical hazards will depend on the type and concentration
of the chemical contaminants, and the characteristics of the area. Isolated upland lakes and drinking-water
reservoirs used for recreational activities are typically protected from chemical contamination. River flows, and
tidal and wave action can dilute and disperse chemical discharges. In contrast, slow-flowing lowland rivers and
lowland lakes may be more susceptible to contamination and provide low levels of dilution or dispersal. Water
bodies subject to continuous or intermittent discharges could accumulate contaminated sediments.

Oil spills and uncontrolled discharges of industrial and mining waste waters have the potential to release
high concentrations of petroleum hydrocarbons and dissolved metals and metalloids. In many cases, spills
and discharges have substantial impacts on aesthetic quality of receiving waters that lead to avoidance by
recreational users.

In most cases, with the exception of spills, unregulated industrial discharges and accidental discharges, chemical
exposures will be well below guideline values in the GDWQ (WHO, 2017), which are based on ingestion of 2 L
of water per day – this is well above ingestion associated with recreational activities.

Excluding algal toxins (refer to Chapter 5), significant concentrations of naturally occurring chemical hazards in
most surface waters are less likely than contamination by industrial, agricultural and municipal pollution. However,
 8. Chemicals 123

small recreational water bodies containing water from mineral-rich strata could contain high concentrations
of some substances under some circumstances. Aesthetic degradation of the water (refer to Chapter 9) is the
most likely scenario – for example, as a result of contamination with metals, such as iron.

Chemical mixtures
Chemicals in natural fresh and marine waters are always present in mixtures. However, separate guideline
values are calculated for most chemicals of public health significance without consideration of additive effects,
and synergistic or antagonistic interactions. For many chemicals, this is appropriate for a number of reasons.
• Differences in mechanisms of toxicity mean that interactions are unlikely.
• The large uncertainty included in the calculation of individual guideline values is considered sufficiently
conservative to account for unexpected interactions.
• It is unusual for hazardous chemicals to be continuously present at concentrations at or near their guideline
values.

Exposures through recreational water are also low and intermittent compared with, for example, exposures
from chemicals in drinking-water.

However, there may be occasions when a number of chemical hazards with similar toxicological mechanisms
are present. In such cases, potential impacts of chemical mixtures need to be considered (WHO, 2017, 2019).
Where necessary, guidance on chemical mixtures in source water and drinking-water (WHO, 2017) can be
applied to recreational water.

Microplastics
Waste plastics make up about 80% of all marine debris. The most visible impacts are effects on marine wildlife,
and aesthetic impacts on beaches and shorelines. Microplastics have been detected at concentrations of 0–10 3
particles/L in fresh water (WHO, 2019). Concentrations in marine water can vary over a wide range; the average
global concentration is estimated as 0.2–0.9 × 10 3 particles/L, and concentrations can be up to 9–16 particles/L
in surface ocean water (Lusher, 2015; Everaert et al., 2018).

A review of microplastics in drinking-water found no evidence of human health risks associated with their
ingestion (WHO, 2019). Levels of exposure to chemicals associated with microplastics in drinking-water are very
small compared with the exposures leading to toxicity, and the relative contribution of pathogens and biofilms
attached to microplastics in drinking-water is insignificant compared with other sources. This also applies to
fresh and marine waters.

The much lower ingestion of water associated with recreational activities compared with drinking-water also
reduces any potential risks associated with microplastics.

8.1.3 Risk assessment

Information on the pattern and type of recreational uses of the water will indicate the degree of contact with
the water, and whether there is a significant risk of ingestion or inhalation of aerosols.
Chemical analysis will be required to support a quantitative risk assessment if contamination is present and there
is significant exposure of users. The sampling programme should take into account variation in contamination
with time and water movement. If resources are limited and the situation is complex, samples should first be
taken at the point considered to give rise to the worst-case scenario; only if this gives rise to concern is there
a need for wider sampling.

Quantitative risk assessments should consider the anticipated exposure in terms of both dose (e.g. whether
there is significant ingestion) and frequency of exposure. The assessment should also consider the form of the
contaminant, particularly for inorganic chemicals. For example, the form of metals detected can significantly
influence solubility and absorption.
124 GUIDELINES ON RECREATIONAL WATER QUALITY — Volume 1: coastal and fresh waters

Example 8.1. Potential PFAS contamination in Australia

Historical use of firefighting foams at Australian Government Air Force bases has been identified as a potential source of per- and
polyfluoroalkyl substances (PFAS) in surface waters. Extensive environmental and health investigations and assessments have been
instigated. Initial risk assessments showed that off-site migration of these substances through groundwater and across-surface
stormwater flows was likely. Streams, drainage channels and impoundments were identified as potential receptors. The water bodies
were generally slow moving in summer, and some were used for swimming and other recreational activities.

The initial assessment found that potential health risks associated with PFAS arise from ingestion; dermal absorption and
inhalation were not considered significant sources of exposure (NHMRC, 2019). Precautionary advice was issued for the public to
avoid recreational contact that might lead to accidental ingestion from potentially contaminated surface waters while investigations
were undertaken. Warning signs were installed.

Health-based guideline values were developed for investigation of potentially contaminated sites in 2016 (Australian Government
Department of Health, 2016). Guideline values for recreational activity (0.7 µg/L for PFOS/PFHxS; 5.6 µg/L for PFOA) were set at 10 times
drinking-water guideline values, based on the approach described in the 2003 WHO Guidelines for safe recreational water environments:
volume 1 – coastal and fresh waters. In 2019, the guideline values were replaced using a more refined analysis of exposure, based on
ingestion volumes per swimming event (200 mL) and a conservative estimate of the annual frequency of swimming events per person
(150 events per year) (NHMRC, 2019). Guideline values were set at 2 µg/L for PFOS/PFHxS and 10 µg/L for PFOA.

The formal setting of guideline values for recreational use of surface waters provided certainty for assessment of public health risks.
Exceedances have been detected in drains and creeks near defence bases, although the number of exceedances has been reduced
by the increase in the guideline value concentrations published in 2019. Exceedances have not been detected in larger bodies of
water, such as coastal waters.

Communities are being informed about results, and advice is issued about surface waters (generally drains and creeks) that are not
suitable for recreational use.

Source: Australian investigations (http://www.defence.gov.au/environment/pfas/).

Except for spills and unregulated discharges, it is unlikely that water users will come into contact with sufficiently
high concentrations of chemical contaminants to cause adverse effects following a single exposure. Even
repeated exposure is unlikely to result in adverse effects at the concentrations of chemicals typically found in
surface water.

Example 8.1 provides a case study relating to surface water contamination with per- and polyfluoroalkyl substances.

Some water bodies will be assessed as being permanently unsuitable for recreational contact – for example,
quarries and abandoned mine pits that have filled with water. These will typically contain high concentrations
of the mineral being extracted, may contain high concentrations of chemicals used in extraction processes,
and can have very high or low pH. Quarry and pit lakes can contain metals (e.g. iron, aluminium, manganese,
lead, copper, cadmium, nickel, zinc) and metalloids (e.g. arsenic, antimony). They can contain water with pH
<3 (Nancucheo et al., 2017; Petrounias et al., 2019), and limestone quarry lakes can contain water with pH
>11. Swimming in waters with pH >11 or <4 can cause irritation of the eyes, skin and mucous membranes.

Chemical spills
Oils spills can release complex mixtures of chemicals, primarily hydrocarbons. Most are not soluble and
spills produce large, visible floating slicks that discourage recreational exposure. A common feature of the
soluble hydrocarbons (e.g. toluene, ethylbenzene, xylenes) is the production of distinctive tastes and odours
at concentrations that are well below those that represent health concerns (WHO 2008, 2017). These tastes
and odours will render water unsuitable for recreational use. Studies of human health impacts of oil spills have
largely focused on impacts on clean-up volunteers and communities living near the site of spills, rather than
exposure through recreational use of the waters (Aguilera et al., 2010).

Uncontrolled discharges from industrial and mine sites can release high concentrations of chemicals such as metals
and metalloids into receiving waters (Nancucheo et al., 2017; Petrounias et al., 2019). Mine wastewaters can
have a pH <3 or >11. Uncontrolled discharges often cause visible and distinct discolouration of receiving waters.
 8. Chemicals 125

8.2 Monitoring
8.2.1 Guideline values
Targeted chemical analyses should be undertaken to support quantitative risk assessments when contamination
is known or suspected (e.g. from industrial discharges, historical contaminated sites or mineral rich strata, if
identified by sanitary surveys).

No specific rules can easily be applied to calculate guideline values for chemical contaminants in recreational
waters that take account of the various degrees and frequencies of contact (e.g. passive, incidental, whole
body) and types of exposure (e.g. dermal, ingestion, inhalation). However, provided that care is taken in their
application, the GDWQ (WHO, 2017) provide a starting point for deriving values that can be used in a screening-
level risk assessment, together with estimates of exposure associated with recreational activities. As discussed
in section 8.1.1.2, ingestion of water when swimming ranges from 1.7 L to 2 L per year in temperate waters and
32 L to 38 L per year in warmer waters. This represents less than 0.3% and 5%, respectively, of the volume of
drinking-water ingested per year. A simple screening approach is therefore to investigate a substance occurring
in recreational water at a concentration 20 times higher than the guideline value in the GDWQ (Table 8.1).

Exceedances do not necessarily indicate that a problem exists. Rather, they suggest the need for a specific
evaluation of the chemical, taking into consideration local circumstances and conditions of the recreational
water area. These could include the types and frequencies of recreational water activities, and the effects of
winds, currents and tides on chemical concentrations.

Table 8.1
Screening values for indicative chemicals in recreational waters

Chemicala Drinking-water guideline value (mg/L) Recreational water screening value (mg/L)
Aluminium 0.9b 18
Arsenic 0.01 (P) 0.2
Benzene 0.01 (P) 0.2
Cadmium 0.003 0.06
Chromium 0.05 (P) 1
Copper 2 40
Ethylbenzene 0.3c 6
Lead 0.01 (P) 0.2
Manganese 0.4 b
8
Nickel 0.07 1.4
Toluene 0.7c 14
Xylenes 0.5 10

P: provisional.
a
No guideline values or health-based values are specified for iron, tin or zinc in the GDWQ.
b
Health-based value.
c
The guideline value exceeds the lowest reported odour threshold.

8.2.2 Operational monitoring

Operational monitoring involves observations and measurements to assess whether control measures are working.
In terms of chemical quality, this could include measures such as:
• monitoring of control of industrial discharges, including treatment, where used, and compliance with
discharge permits (including flow rates);
126 GUIDELINES ON RECREATIONAL WATER QUALITY — Volume 1: coastal and fresh waters

• monitoring fencing and signage installed to prevent access to water bodies such as quarry lakes that are
permanently unsuitable for recreational use;
• monitoring implementation of good management practices associated with use of agricultural chemicals;
and
• monitoring of soil and underlying groundwater downstream of historical contaminated sites.

8.3 Management and communication

Pollution events should be managed, and timely and effective communication should be provided about
recreational water environments affected by chemical hazards. If changes are detected in water quality as a
result of pollution events, multifaceted approaches will generally be needed to provide public health advisories,
including:
• issuing of media advice
• communication with community or residents’ groups
• installation of signage and its maintenance (e.g. in the event of vandalism).

Information should be provided on:

• the cause and nature of contamination
• the basis for assessing risks, including the source of guideline values applied
• activities to be avoided
• potential health risks
• remedial action.

Where waters have been assessed as being permanently unsuitable for recreational use, it is essential that the
public is informed and regularly reminded of the risks associated with water contact. If fencing is installed to
prevent access, it needs to be regularly checked and maintained; signage also needs to be maintained.

Management of pollution events will be influenced by the type and form of contamination. For example, spills
can entail shorter-term responses, with a focus on clean-up and remediation. Management may be driven by the
need to mitigate environmental impacts rather than public health impacts and will be directed by environmental
protection agencies. Detection of potentially persistent events, such as pollutants being carried from sites
separated from water bodies, will require much longer remediation strategies, even after the polluting activity
ceases. These are also likely to be directed by environmental protection agencies.

8.4 Research needs

More data are needed on volumes of water ingested and inhaled during various recreational activities (e.g.
swimming, waterskiing), and on frequencies of exposure in temperate, subtropical and tropical settings.

Research is also needed into dermal exposure to chemicals in recreational water with the potential to cause skin
rashes and eye irritation; many reports on these reactions are anecdotal. Research could specifically examine
whether wearing of wetsuits increases the risk of skin irritation and the absorption of chemicals through the skin.
 8. Chemicals 127

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