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Arsenic in Geothermal Waters

Peter Cressey
ESR

Peer review:
Dr Chris Nokes
ESR

1. Arsenic intoxication following bathing in a geothermal hot pool

Background

A claim has been made that bathing in a geothermally-fed hot pool has resulted in arsenic
poisoning. This claim is supported by analyses of arsenic in hair and analysis of the pool
water:
http://www.garymoller.com/single-post/2017/03/11/Is-bathing-in-Central-North-Island-
thermal-water-endangering-your-health

The incident occurred in Tokaanu, at the southern end of Lake Taupo, which is within the
Taupo Volcanic Zone (TVZ).

The following sections will examine the evidence supporting this claim and provide
information and assessment to allow the plausibility of this claim to be examined.

Is the reported arsenic concentration in the hot pool likely?

The author of the article (Mr Gary Moller) had a sample of water from the hot pool analysed
by Eurofins ELS Ltd, with an analytical result for arsenic of 1.59 mg/L reported. Eurofins are
a suitably competent laboratory to perform this analysis.

It is unknown whether the water in the hot pool came directly from a geothermal source or
whether it was mixed with other water. Two studies were found that reported arsenic
concentrations in geothermal waters from the TVZ. Hug et al. (2014) reported arsenic
concentrations in the range 2.9-4.2 mg/L in Champagne Pool, part of a geothermal complex
at Waiotapu, between Taupo and Rotorua. Lord et al. (2012) reported arsenic concentrations
in the range 0.008-9.08 mg/L in 28 features from the TVZ. The highest concentrations found
in this study (8.59, 8.70 and 9.08 mg/L) were from features in the Tokaanu area.

It is very likely that the concentration of arsenic in the hot pool was about 1.5 mg/L. It is also
possible that this concentration resulted from dilution of a geothermal water source
containing even higher arsenic concentrations.

How could arsenic exposure have occurred?

There are three main routes that toxic substances may enter the body and elicit a toxic
response (poisoning); orally by ingestion and absorption from the gastrointestinal tract, by
inhalation of airborne toxicants and absorption from the lungs, and dermally, by direct
absorption through the skin into the bloodstream.
The picture of the pool, shown in the on-line article, suggests that the pool is suitable for
bathing, but not swimming. Under these circumstances ingestion or inhalation of pool water
is likely to be at a low level (see below for more detail), with dermal exposure being the more
likely route of exposure.

Is arsenic dermally absorbed?

The most comprehensive source of information on the toxicity of arsenic is the toxicological
profile prepared by the US Agency for Toxic Substances and Disease Registry (ATSDR)
(ATSDR, 2007). ATSDR note that there is little human or animal information on toxicity
following dermal exposure to arsenic. While it should be remembered that absence of
evidence is not evidence of absence, the lack of human case reports of toxicity following
dermal exposure suggests that dermal absorption of arsenic is probably low. This is
supported by a limited number of rodent studies that showed no adverse effects following
dermal exposure dose of 1000 mg/kg bw/day of monomethyl arsonic acid or dimethyl arsinic
acid.

Studies with human cadaver skin found <1% of a dermal arsenic dose passed through the
skin over 24 hours (Wester et al., 1993). This compares to estimates of absorption following
inhalation or oral ingestion of 50-100% (ATSDR, 2007).

While it is not possible to draw a definitive conclusion on the possibility of arsenic


intoxication following dermal exposure, the lack of case reports of intoxication following
dermal exposure and the apparent low rate of dermal absorption suggests this is unlikely.

Is poisoning due to oral exposure likely?

While bathing, there is potential for inadvertent ingestion of water and associated exposure
to arsenic. While studies have reported significant ingestion of water during swimming
(Dufour et al., 2006; Evans et al., 2006; Suppes et al., 2014), ingestion during hot pool
bathing is likely to be considerably lower and probably similar to wading or splashing in
water. In a study investigating self-reported water ingestion during various recreational
activities, 97.3% of respondents did not report ingestion of any water during wading or
splashing (Dorevitch et al., 2011). The remaining respondents (2.7%) reported ingesting up
to a teaspoon of water, but none reported ingesting as much as a mouthful. The same study
determined that this level of ingestion equated to a mean of 10.8 mL of water.

In the Tokaanu incident, if it is assumed that 10.8 mL of water was ingested, containing 1.59
mg/L arsenic, and that this water was ingested by a New Zealand woman of average body
weight (about 75 kg), the resulting exposure dose would have been 0.0002 mg/kg bw (0.2
g/kg bw). This is approximately the same as the estimated average daily exposure of New
Zealand women to inorganic arsenic1 from the diet (Vannoort and Thomson, 2011). ATSDR
have defined a minimal risk level (MRL) for acute duration (14 days or less) arsenic
exposure of 5 g/kg bw/day; 25 times the hypothetical exposure level in the current incident.

1 Arsenic occurs in both organic and inorganic forms, with the organic forms of
much lower toxicity than the inorganic forms. The total exposure to arsenic
(organic and inorganic) from the diet is about an order of magnitude higher than
the exposure to inorganic forms.
How should the hair arsenic levels be interpreted?

Measures such as the concentration of arsenic in hair, blood or urine are collectively referred
to as biomarkers of exposure. Depending on the absorption, distribution, metabolism and
excretion (ADME) of a chemical, biomarkers may be representative of recent exposure or
long-term (chronic) exposure. As arsenic is cleared from the blood within a few hours, this is
considered to be a biomarker of very recent exposure only (ATSDR, 2007). Arsenic tends to
accumulate in hair and nails, and measurement of arsenic levels in these tissues may be a
useful indicator of past exposures. Concentrations of arsenic in hair or nails may increase
from several-fold to several hundred-fold following arsenic exposure. However, analysis of
hair may yield misleading results due to the presence of arsenic adsorbed to the external
surface, as analyses are unable to distinguish such arsenic from arsenic accumulating in the
hair due to internal exposure (ATSDR, 2007; EFSA, 2009).

Once hair arsenic concentrations become elevated due to oral arsenic exposure, they have
been reported to remain elevated for 6-12 months (ATSDR, 2007). While it is not entirely
clear from the article, it appears that the cases hair arsenic decreased substantially after
several months.

It is quite likely, and even probable, that the high arsenic concentrations found in hair in the
current incident were a result of direct contact of the hair with the arsenic-containing water.
This hypothesis is also consistent with the decrease seen in hair arsenic after avoiding
bathing in hot pools repeated washing of the hair would have gradually removed the
adsorbed arsenic from the surface of the hair.

Were the observed symptoms consistent with arsenic intoxication?

While it is not completely clear from the internet article, it appears that there was a single
incident of bathing in the Tokaanu hot pools. As such, the symptoms seen should have been
consistent with an acute intoxication, rather than chronic exposure to arsenic.

Mr Moller states that the symptoms of arsenic toxicity center around chronic fatigue, aching
muscles, aching joints, sore tendons, rapid onset of arthritis, various connective tissues
disorders, including frozen shoulder and tendon contractures, thyroid issues, poor hair, skin
and nails, brain fog, viral infections and a long list of immune related disorders, such as
rheumatoid arthritis, psoriatic arthritis and psoriasis. These symptoms are mainly indicative
of neurotoxicity and immunotoxicity. However, it should be noted that these are not the
symptoms usually associated with acute arsenic intoxication.

Acute arsenic intoxication usually starts with gastrointestinal symptoms (diarrhoea, vomiting,
abdominal pain), progressing to multiple organ damage, with damage to the blood-forming
systems, the liver and the kidneys having been noted (ATSDR, 2007). Cardiovascular
symptoms have also been reported. While neurological effects have been reported in some
cases, these are typically peripheral neuropathy; numbness or pins and needles in the
extremities. Suppression of the immune system or other immunotoxicological symptoms
have not been reported in human cases or in animal studies. There have been very
occasional reports of effects on the endocrine systems, but these appear to be associated
with the pancreas, rather the thyroid gland.

The symptoms of arsenic toxicity reported by Mr Moller presumably include the symptoms
exhibited by his partner. Based on the scientific literature, these symptoms are not typical of
acute arsenic intoxication.
Conclusions

The hot pool at Tokaanu contained elevated concentrations of arsenic, which is consistent
with other information on arsenic levels in geothermal water in the TVZ. However, the
potential exposure to arsenic from bathing in this pool and the reported symptoms are
inconsistent with acute arsenic intoxication. The elevation in hair arsenic for the case is likely
to have been due to direct contact of the hair with pool water, rather than systemic transfer of
arsenic to hair. Further information on the time between exposure and the taking of the hair
sample may help to clarify this point.

2. Arsenic contamination of the Waikato River

Background

An internet article discussed levels of arsenic in Lake Maraetai, on the Waikato River
system, and presents a case study of a family with a holiday home in Mangakino who bathed
in the lake:
http://www.garymoller.com/single-post/2017/01/22/Is-the-Waikato-River-a-public-health-
hazard-due-to-arsenic-contamination

The case study includes analysis of arsenic in hair from the family and reported, but
unspecified, ill health.

The article also infers risks associated with Aucklands drinking-water supply due to arsenic
in the Waikato river system.

Is the reported concentration of arsenic in Lake Maraetai likely?

The article reports an arsenic concentration in water from Lake Maraetai of 0.026 g/m3
(0.026 mg/L or 26 g/L). The article incorrectly identifies the drinking-water official limit as
0.001 g/m3 (0.001 mg/L or 1 g/L). The maximum acceptable value (MAV) for arsenic in
drinking-water in New Zealand is 0.01 mg/L.

A year-long study of arsenic concentrations in the Waikato River reported a mean


concentration at Hamilton (downstream from Lake Maraetai) of 32.1 g/L (McLaren and Kim,
1995). This is consistent with the arsenic concentration measured at Lake Maraetai. The
study of McLaren and Kim demonstrated a distinct seasonal effect, with arsenic
concentrations in the summer months reaching concentrations as high as 60 g/L. An
arsenic concentration of 42.7 g/L was determined in Lake Ohakuri, just upstream from Lake
Maraetai. Another study reported similar results, with summer arsenic concentrations at
three points on the Waikato River (Hamilton, Pukerimu and Lake Karapiro) in the range 25-
29 g/L and winter concentrations in the range 16-18 g/L (Gregor, 2001).

On the basis of the available studies, the concentration of arsenic measured in Lake
Maraetai is extremely likely.

Arsenic reduction during treatment of Waikato River water

The article asserts that We are not aware of any processing during the "treatment" of this
water to remove heavy metals, including arsenic which is present in the Waikato River.
The study of McLaren and Kim examined the arsenic concentration of water in the Waikato
River at Hamilton and in Hamilton reticulated water following full conventional water
treatment (McLaren and Kim, 1995). In this study, conventional water treatment decreased
water arsenic concentrations from a mean of 32.1 g/L to 6.2 g/L; an approximately six-fold
reduction.

A more detailed analysis of arsenic removal at three treatment plants (Hamilton city,
Pukerimu and Lake Karapiro) demonstrated changes in the form of arsenic present in water
and removal of arsenic, mainly during aluminium-based coagulation (Gregor, 2001). Arsenic
removal was greater than 80% in most cases studied. It should be noted that Pukerimu and
Lake Karapiro are small water treatment plants, serving communities of 3000 and 10,000
people, respectively, at the time the paper was published.

With respect to the Auckland water supply, Watercare publishes an annual summary of water
quality testing carried out at all of the water treatment plants in the Auckland region. The
most recent report (1 July 2015 to 30 June 2016)2 reported results of 13 arsenic analyses
carried out on treated drinking-water from Watercares Waikato water treatment plant; the
treatment plant that treats Waikato river water for supply to Auckland city.3 The mean
concentration of arsenic was 0.4 g/L, with a maximum of 1.9 g/L.

There is evidence that even quite basic water treatment can reduce arsenic concentrations
by more than 80%. There is further evidence that water from the Waikato River, following
treatment at the Waikato water treatment plant contains acceptably low concentrations of
arsenic.

What can be concluded from the evidence provided with respect to the Lake Maraetai
family?

A family of four (father, mother and two children) were reported to bath in Lake Maraetai and
all had subtle health problems that were consistent with arsenic toxicity, principally varying
degrees of unusual fatigue. Hair from all family members was tested and found to contain
elevated concentrations of arsenic. The family decided to avoid bathing in the lake and after
several months the fathers hair arsenic levels were unchanged. Hair from other family
members was not retested. The author of the article noted that There has been a noticeable
improvement in the health and energy of all the family members, especially the mother who
was the most unwell by far.

As noted earlier in the current report, arsenic binds strongly to the keratin protein that hair is
composed of. If the family members had been bathing in the lake, hair arsenic levels would
almost certainly be elevated due to this. However, binding of arsenic to the exterior surface
of the hair has no toxicological implications. It is possible that ingestion of arsenic also
contributed to the hair arsenic concentrations. However, it has been reported that ingestion
of drinking-water containing 50-120 g/L of arsenic resulted in only a marginal effect on hair
arsenic (ATSDR, 2007). It is unlikely that the amounts of water ingested during bathing and
the concentration of arsenic in the water (26 g/L) would have resulted in a measurable
increase in hair arsenic. It is uncertain whether the lack of decrease in the fathers hair
arsenic concentration was due to the persistence of surface-bound arsenic or due to
ingested arsenic from other sources.

2
http://www.watercare.co.nz/SiteCollectionDocuments/AllPDFs/Annual_Water_Quali
ty_Report_2015-2016.pdf Accessed 18 May 2017

3 https://www.watercare.co.nz/about-watercare/our-services/waikato-river-water-
treatment/Pages/default.aspx Accessed 23 May 2017
While the author of the article states that the familys symptoms were consistent with
exposure to arsenic, only unusual fatigue was reported as a symptom. As noted in Part 1 of
this report, the symptoms noted by the author of the article as being typically of arsenic
exposure are not symptoms of arsenic intoxication reported in human case studies.

Given that the presence of arsenic in hair samples from the family is consistent with having
bathed in water containing elevated concentrations of arsenic and the lack of specific
reported health symptoms consistent with arsenic intoxication, there is little that can be
concluded from this case study.
References
ATSDR. (2007) Toxicological profile for arsenic. Atlanta, Georgia: Agency for Toxic
Substances and Disease Registry.

Dorevitch S, Panthi S, Huang Y, Li H, Michalek AM, Pratap P, Wroblewski M, Liu L, Scheff


PA, Li A. (2011) Water ingestion during water recreation. Water Research; 45(5): 2020-2028.

Dufour AP, Evans O, Behymer TD, Cantu R. (2006) Water ingestion during swimming
activities in a pool: a pilot study. Journal of Water and Health; 4(4): 425-430.

EFSA. (2009) Scientific opinion on arsenic in food. EFSA Panel on Contaminants in the
Food Chain (CONTAM). EFSA Journal; 7(10): 1351.

Evans O, Wymer L, Behymer T, Dufour A. (2006) An observational study: Determination of


the volume of water ingested during recreational swimming activities. Poster presented at
the National Beaches Conference, Niagara Falls, New York. Washington, DC:

Gregor J. (2001) Arsenic removal during conventional aluminium-based drinking-water


treatment. Water Research; 35(7): 1659-1664.

Hug K, Maher WA, Stott MB, Krikowa F, Foster S, Moreau JW. (2014) Microbial contributions
to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New
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Lord G, Kim N, Ward NI. (2012) Arsenic speciation of geothermal waters in New Zealand.
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McLaren SJ, Kim ND. (1995) Evidence for a seasonal fluctuation of arsenic in New
Zealand's longest river and the effect of treatment on concentrations in drinking water.
Environmental Pollution; 90(1): 67-73.

Suppes LM, Abrell L, Dufour AP, Reynolds KA. (2014) Assessment of swimmer behaviors on
pool water ingestion. Journal of Water and Health; 12(2): 269-279.

Vannoort RW, Thomson BM. (2011) 2009 New Zealand total diet study. Agricultural
compound residues, selected contaminant and nutrient elements. Accessed at:
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Wester RC, Maibach HI, Sedik L, Melendres J, Wade M. (1993) In vivo and in vitro
percutaneous absorption and skin decontamination of arsenic from water and soil.
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