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Plumbosolvency exacerbated by Water Fluoridation

Authors:

Abstract

Plumbosolvency, the dissolution of metallic Lead, which results in the contamination of drinking water and consequent damage to human health, is recognized as a major problem wherever Lead pipes, solder or brass fittings are present in the supply route. Plumbosolvency is exacerbated by Fluoridation of drinking water. The use of Phosphate in an attempt to reduce the dissolution rate leads to increased costs, waste of a scarce natural resource and environmental degradation. Immediate cessation of neurotoxic Fluoridation to reduce plumbosolvency makes more economic sense. Provision of communal water supplies from point of collection reverse osmosis filters can bring an immediate end to Lead exposure while sources of Lead contamination are gradually removed from the supply network, creating thousands of person years employment in a depressed economy.
Plumbosolvency exacerbated by Water Fluoridation
Geoff Pain
September 2015
Abstract
Plumbosolvency, the dissolution of metallic Lead, which results in the contamination of drinking water and
consequent damage to human health, is recognized as a major problem wherever Lead pipes, solder or brass fittings
are present in the supply route. Plumbosolvency is exacerbated by Fluoridation of drinking water. The use of
Phosphate in an attempt to reduce the dissolution rate leads to increased costs, waste of a scarce natural resource
and environmental degradation. Immediate cessation of neurotoxic Fluoridation to reduce plumbosolvency makes
more economic sense. Provision of communal water supplies from point of collection reverse osmosis filters can
bring an immediate end to Lead exposure while sources of Lead contamination are gradually removed from the
supply network, creating thousands of person years employment in a depressed economy.
Keywords: Crime, Delinquency, Fluoride, Fluoridation, Heart, Hexafluorosilicate, IQ, Lead, Neurotoxin, Phosphate,
Plumbosolvency, Stroke
Introduction
The historical use of the malleable metal Lead in plumbing has left a toxic legacy that will cost many nations billions
of dollars to remove. In the presence of oxygen, Lead will dissolve slowly with the initial formation of Lead
Hydroxide, which readily reacts with other ions. With Carbonate or Chloride, slightly soluble salts form a crust on the
metal. The following Table of Solubility shows relative solubilities for some Lead compounds [CRC].
Compound
Formula
Solubility in Cold (20oC) Water
Gram per litre
Lead Hexafluorosilicate
PbSiF6

Lead Chloride
PbCl2
0.99
Lead Fluoride
PbF2
0.64
Lead Fluorochloride
PbFCl
0.37
Lead Oxychloride, the mineral
Matlockite
PbCl2.Pb(OH)2
0.0095
Lead Carbonate, the mineral
Cerussite
PbCO3
0.0011
Lead Orthophosphate
Pb3(PO4)2
0.00014
Basic Lead Carbonate, White
Lead
2PbCO3.Pb(OH)2

EU 2013 Target
0.00001
USEPA Minimal Risk Level
0.0000001

0
The addition of Chlorine to water could in theory reduce leaching by formation of Matlockite, but is more likely to
increase leaching of Lead by forming Lead Chloride. Chlorine also leads to formation of Chloramines which enhance
leaching of brass, releasing more Lead [Miranda 2006, Switzer 2006, Maas 2007].
Governments 
advent of the European Union, multinational standards for water safety have emerged and member nations have
found themselves confronted with the obligation to try to meet those standards.
The EU set a target of less than 10 micrograms of Lead per litre (10 ppb) to be reached by 2013. The optimum level is
Zero ppm.
Adverse Effects of Lead
It took decades of consumer activism to eliminate tetraethyllead from petrol despite decades of scientific proof of
harm. Like Fluoride, Lead is bio-accumulative, both being recognized neurotoxins that permanently damage the
brain, reducing IQ [Xiang 2003] and can cause behavioural problems. Mullinex [1995] found fluoride more potent
than lead in damage to behaviour of experimental animals. Therefore the apparent concern over Lead
contamination tends to obscure the neurotoxic hazard of Fluoride in public discussions of water contamination
[Xiang 2003]. Recently the United States halved the market for Fluoride by reducing the concentration of Fluoride in
US water supplies to 0.7 ppm [Gooch 2015].
Lead increases the severity of dental fluorosis. Increased body load of Lead reduces IQ [Masters 2004, Lamphear],
decreases learning ability [Niu 2008, 2009], increases juvenile delinquency, and increases crime rates [Mann 2000].
Fetal death and reduced birth rates are associated with exposure to lead-contaminated drinking water [Edwards
2014].
Lead is also associated with high blood pressure, stroke and heart attacks [Pocock 1998].
Hexafluorosilicate increases Lead leaching
Hydrofluorosilicic acid and its salts are waste products from the phosphate fertilizer industry that cannot be legally
dumped on land, surface water, groundwater or the sea. The compound reversibly hydrolyses forming oligomers.
Presence of excess silica stabilizes hexafluorosilicate ion and its partial hydrolysis products [Borodin 1974].
Hydrofluorosilicic acid (H2SiF6) doubles the number of children with blood Lead (PbB) > 10 mg/dL [Coplan 2007].
The addition of Hydrofluorosilicic acid has been demonstrated to increase the dissolution rate and hence the
concentration of Lead in drinking water supplies and this translates directly to higher Lead blood levels and
associated human damage [Masters 2000, Allegood 2005, Clabby 2006 and Miranda 2006, discussed in Maas 2007].
This occurs because Hexafluorosilicate can form complex ions with Lead ions (coordination number up to nine) via
bridging Fluorine atoms in solution [Bonomi 2001, Burt 2015, Cole 1981]. Stable Hexafluorosilicate compounds are
readily obtained from aqueous solution [Conley 2002, Gelmboldt 2007, Burt 2015].
Rapid ion exchange causes shifts in 19F NMR measurements and has led some researchers to mistakenly state that
hydrolysis of hexafluorosilicate is complete in water. However the fact that Si-F coupling constants are observed at
low temperature confirms attachment of F to Si under mild conditions [Borodin 1974, Conley 2002].
There is also a little studied Pentafluorosilicate ion SiF5- that is present at pH below 3.5 [Finney 2006]. The hydrated
ion [SiF5(H2O)] and the neutral intermediate trans-[SiF4(H2O)2] have been successfully isolated in stable solids
[Gelmboldt 2007]. The stability of complex fluoride ions of silicon is enhanced by the fact that the Si-F bond is much
stronger than the Si-O bond [CRC]. The toxicology of these fluorosilicate species has not been widely reported [Rice
2014], and perhaps even suppressed. According to one study No carcinogenicity studies have been conducted using
(hydro)fluorosilicic acid, sodium silicofluoride, disodium hexafluorosilicate or hexafluorosilicate or hexafluorosilicic
acid. [European Commission 2010].
Hydrofluorosilicic acid is a more powerful inhibitor of acetylcholinesterase than Sodium Fluoride (NaF) [Westendorf
1975, cited in Coplan 2007].
Use of Phosphate in attempts to reduce Plumbosolvency
Some water suppliers have added Orthophosphate in an attempt to counter the leaching by formation of a thin
coating of Lead Orthophosphate inside the pipes [Comber 2011]. However reference to the Table of Solubility above
shows that, assuming saturated conditions, the EU target will clearly not be met by this treatment because any Lead
Phosphate in the pipes has plenty of time to dissolve to reach saturation when the water is not flowing.
Phosphorus is essential to life but is a rapidly diminishing natural resource and should therefore be conserved for
food production. Given that 99% of the added Phosphate will not be consumed by humans, the economic and
environmental folly of this approach is exposed.
When excess Phosphorus is released to the environment, algal blooms can occur that damage the ecology and
dosing concentrations commonly used in attempts to reduce plumbosolvency are up to 30 times those allowed in UK
rivers [Gooddy 2015].
Phosphate sources commonly used are Phosphoric Acid or Monosodium dihydrogenphosphate (about seven times
the cost of the acid). Zinc phosphates would be too toxic to contemplate. It has been found that some
Polyphosphate chemicals actually increase Lead mobilization [Edwards and McNiell 2002 cited in Maas 2007].
All Phosphate sources are contaminated with toxic and carcinogenic elements including Arsenic, Cadmium,
Chromium, Copper, Lead, Mercury, and Zinc. Clearly the addition of Phosphate increases risk to human health.
In a 2003 study of orthophosphate dosing [Jackson 2003], there was a statistically marginal reduction of measured
Lead in only 3 out of 5 properties tested, however the fundamental flaw of that study was failure to monitor
temperature on sample collection. Following poor results with orthophosphate a 2011 report [UK Water 2011]
discussed the options for finding alternative strategies and briefly mentioned introduction of pipe liners. The
economic model included an estimate of extra costs at waste water treatment plants to cope with the excess
phosphate but failed to include environmental impact and associated costs of dumping phosphate in rivers.
A recent study of orthophosphate dosing performed for the Government of Alberta, Canada, concluded that the
most cost-effective approach for Calgary is an accelerated programme of total pipe replacement, while
orthophosphate will delay the inevitable need to replace pipes in Edmonton [Hayes 2014].
Plumbosolvency Lead Hazard Reduction by Cessation of Fluoridation
Studies in two US cities, Tacoma, Washington and Thurmont, Maryland, found an immediate reduction of Lead
concentration when Fluoridation was stopped. In Tacoma the level dropped from 32 parts per billion (ppb) to 17 ppb
and in Thurmont from 30 ppb to 7 ppb, that is below the 2013 EU target level [cited in Maas 2007].
Recommended actions and alternative Strategy
Considering the available information, the following actions could partially ameliorate the Plumbosolvency threat
from supply networks:
Immediate cessation of Fluoridation
no addition of Phosphates
minimal use of Chlorine
use Ozone instead of Chlorine
adjustment of pH with the least contaminating alkali available
acceleration of Lead pipe replacement
Replacement of piping in the distribution network and customer premises will take time, generating much new
employment and net economic growth. The improvement in human health could be assigned a monetary value.
In order to more rapidly remove this dangerous Lead exposure from the entire affected population, namely those
who drink distributed system water, I suggest an alternative strategy.
As 99% of the system water is not consumed, it would be economically feasible to deliver reverse osmosis pure
water at community taps so that each family could collect a few litres of water per day for drinking and cooking.
The installation requires a small footprint, could be powered by renewable energy and would need a small holding
tank while producing pure water by pressure sensing pump on demand. Citizens would be advised to refill their own
approved container, avoiding plastic waste.
This strategy has been implemented in New Zealand by communities that reject deliberate poisoning of water with
Fluoride, enabling them to opt out at almost no cost apart from transport to the supply point. People are happy to
meet at the clean water tap, similar to distribution of hot water in poorer areas of Scotland, prior to the Thatcher
era.
It would be worthwhile if all water providers immediately installed a number of these facilities for a demonstration
and trial of community acceptance while explaining the real and present danger of Lead poisoning wherever
plumbosolvency occurs.
Hopefully the international attention currently being brought to plumbosolvency will see more governments making
the decision to cease fluoridation of water (as did Israel in 2014) to remove another neurotoxic hazard.
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... Analysis of a US national sample of over 4,000 children in NHANES III, showed that water fluoridation is associated with a significant increase in children's blood lead, with especially strong effects among minority children [Coplan 1999]. This Fluoride enhanced Plumbosolvency is discussed in more detail elsewhere [Pain 2015]. ...
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The observed large reduction in dental caries incidence worldwide since the 1970s is shown to correlate with reduction in airborne Lead due to phase-out of Tetraethyl Lead use in gasoline. This accounts also for the fact that there is no discernible difference in dental decay rates between nations that suffer Fluoridation and those where it is banned. The deliberate addition of Lead as a major contaminant of phosphate fertilizer industrial waste used in Fluoridation plus the exacerbation of Plumbosolvency by Fluoride must cease if further reduction in tooth decay and co-morbidity is to be accomplished.
... Fluoride is a bioaccumulative endocrine disruptor with no nutritional value [Pain 2015a, Pain 2017a. HFSA is known to increase plumbosolvency, the leaching of Lead from brass [Pain 2015b] which leads to all the diseases caused by Lead poisoning, including damaged teeth. Blood lead concentrations in pregnant women are a major risk factor for preeclampsia, with an increase of 1 μg/dL Lead/blood associated with a 1.6% increase in likelihood of preeclampsia, the strongest risk factor for preeclampsia yet reported [Poropat 2017]. ...
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The people of Port Macquarie Hastings in the state New South Wales, Australia, voted overwhelmingly against Fluoridation of their drinking water but their wishes were ignored due to political pressure to aid the disposal of industrial waste from the Phosphate Fertilizer industry. The water supply is drawn from the Hastings River and the project is unusual due to storage of unfiltered Fluoridated water in interconnected earth dams exposed to sunlight. No environmental impact assessment was performed before the project despite the presence of threatened, vulnerable and endangered wildlife in the catchment area. Risks to public health from organic molecules containing Fluorine manufactured by bacteria and algae appear never to have been considered.
... Fluoride exacerbates plumbosolvency, which I have reviewed [Pain 2015d]. ...
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New Zealand Parliament should pass a law to immediately end Water Fluoridation in New Zealand because: The World Health Organization ranks Fluoride toxicity between that of Lead and Arsenic and recognizes Fluoride as a Low-Dose Endocrine Disruptor. Proponents of Fluoridation variously have been conned, follow like sheep, are morally and intellectually bankrupt and in denial of the science, and/or have vested interest. Fluoride harms are admitted behind closed doors and the whistle has blown. Tooth decay is caused by creation of acid from sugars and starch in plaque and real reduction in tooth decay can be achieved by facing the facts. Fluoride is a bio-accumulative systemic poison with no nutritional value. New Zealand clinical trials and mass medication experiments with Fluoride have failed. Fluoridation does not prevent tooth decay but does damage teeth. Industrial waste Fluoride must be immobilized at source to prevent further pollution of New Zealand soil and food. Industrial waste Fluoride delivers other sensitizers and carcinogens to the body. Human rights are paramount. Vulnerable groups in society and the unborn must be protected from harm. Ceasing Fluoridation is the honourable, clever and economic thing to do. New Zealand should join 95% of humanity who have already made the right decision. Recommended further actions by the New Zealand Parliament: New Zealand should commence a judicial review of its involvement with Food Standards Australia and New Zealand, an organization that has recklessly perpetuated the myth that Fluoride is a nutrient. New Zealand must ban sale of all Fluoride “supplements”. New Zealand should ban all human trials where Fluoride is used, overriding any University “ethics approval”. The target for Fluoride intake should be as low as reasonably achievable (the ALARA principle) as with any poison. New Zealand should set new, lower limits on residual Fluoride in phosphate fertilizer.
... It is well known that Lead levels in drinking water are increased by the presence of fluoride, a process known as plumbosolvency [Mahaffey 1976;Masters 2000;Bernard 2003;Burgstahler 2003;Macek 2006;Coplan 2007;Maas 2007;Niu 2008a,b;Niu 2009;Leite 2011;Luo 2011;CDC 2013a;Niu , 2015bPain 2015c]. ...
Technical Report
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Fluoride is a developmental neurotoxin that has been linked to human brain damage since the 1920s when Fluoride induced cretinism was investigated and confirmed with animal studies. With advances in imaging, chemical analytical techniques including proteomics, detailed molecular mechanisms of Fluoride damage to the brain, spinal cord and nerve networks have been investigated with ever increasing levels of detail. The current peer-reviewed scientific publication rate regarding Fluoride neurotoxicity is about one paper per week. This literature guide provides a snapshot of the science as easily obtained in early 2017, to help inform those interested in the depth of knowledge and where the ongoing studies are directed.
... Fluoridation of public drinking water directly raises the amount of Lead intoxication of the unwitting population through the process of Plumbosolvency [Pain 2015c]. Fluoride enhances sudden death by Lead intoxication. ...
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Fluoride uptake in coronary arteries is associated with an increased cardiovascular risk of sudden death. Fluoride causes enhanced deposition of doped Hydroxyapatite which leads to inflammation and sites for fatty deposits of atherosclerosis. Fluoride interferes with numerous enzyme systems resulting in elevation of key risk factors for cardiovascular disease. Fluoride causes oxidative stress and degeneration of heart muscle. Fluoride inhibits Thyroid function with consequential damage to heart function. Fluoride increases risk of sudden death from ruptured aorta. Diabetes, caused or exacerbated by Fluoride, further increases risk of cardiovascular death and disability.
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In 2017 the Australian National Health and Medical Research Council (NHMRC) released a draft information paper on the health effects of water Fluoridation that completely ignored thousands of peer-reviewed scientific publications regarding Fluoride toxicity, by using contrived exclusion criteria and time limits. Similar tactics were employed by the NHMRC in its Fluoridation review published in 2007. This submission, one of the 32 made public, formally records some of the science that has been deliberately ignored.
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An extensive list of scientific references submitted to the New Zealand Parliamentary Inquiry into water Fluoridation.
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Australia's National Health and Medical Research Council states that the only harm arising from water Fluoridation and total dietary Fluoride intake is Dental Fluorosis. This guide provides a quick reference to harms known by toxicologists to be caused by Fluoride, including those still under intensive research and recognized by other administrations.
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Fluoride, Asbestos, Uranium, Lead and Tobacco (FAULT) are multibillion dollar industries that have caused immeasurable harm to humans who have recently discovered that decades of propaganda claims that the products are “safe and effective” are demonstrably false. Each of these industries has a history of denial of harm, suppression of evidence, attempts to avoid litigation and compensation of victims. In a last ditch attempt to retain public drinking water as a conduit for disposal of Fluoride, an industrial waste product, myth-mongers are attempting to promulgate the “Big Lie” that Fluoride is a nutrient.
Article
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Rare examples of phosphine complexes of lead(II) are reported. The reaction of Pb(NO3)2 with Me2P(CH2)2PMe2, o-C6H4(PMe2)2 or Et2P(CH2)2PEt2 (LL) in H2O/MeCN gave white [Pb(LL)(NO3)2], irrespective of the ratio of reagents used. The X-ray structures of [Pb{Me2P(CH2)2PMe2}(NO3)2] and [Pb{o-C6H4(PMe2)2}(NO3)2] reveal chelating diphosphines and κ2-NO3─ groups occupying one hemisphere about the lead centre with single oxygen bridges to two further nitrate groups from neighbouring molecules completing a distorted eight-coordinate geometry. Using Pb(SiF6)⋅2H2O produced [Pb{o-C6H4(PMe2)2}(H2O)(SiF6)]⋅H2O which has a chelating diphosphine, the water molecule and a coordinated SiF62 group (which could be described as either κ1- or asymmetric κ3-coordinated to the lead), with further PbF interactions to neighbouring molecules producing a chain polymer structure. The structure of [Pb{o-C6H4(PMe2)2}(DMF)2(SiF6)]⋅DMF was also determined and contains dimers with fluorosilicate bridges. Adventitious oxygen readily forms of diphosphine dioxide complexes, and the structures of [Pb{Et2(O)P(CH2)2P(O)Et2}2(NO3)2] and [Pb{Me2P(CH2)2PMe2}{Me2(O)P(CH2)2P(O)Me2}]- [BF4]2⋅½MeNO2 produced in this way were determined. The former contains eight-coordinate lead with κ2-NO3 groups and bridging diphosphine dioxides, which results in an infinite polymer, whilst in the latter the diphosphine is chelated but the diphosphine dioxide bridges between Pb(II) centres, with coordinated BF4 groups completing a very distorted ten-coordinate moiety. Attempts to isolate similar complexes with o-C6H4(PPh2)2 or o-C6H4(AsMe2)2 were unsuccessful.
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Co-existing as environmental pollutants in certain areas of China where lead (Pb) is mined, fluoride (F) and Pb pose serious risks to the human central nervous system (CNS). Calcium/calmodulin-dependent protein kinase II (CaMKII) expression, which is involved in the process of learning and memory, has an important role in CNS functioning. Here, in order to verify whether F and/or Pb affect CaMKII expression, we determined the CaMKII expression level in the hippocampus of rats administered 150 mg sodium fluoride/L and/or 300 mg lead acetate/L in their drinking water for 30 days. Through quantitative positioning analysis by western blotting and immunofluorescence, respectively, CaMKII expression levels in the F, Pb, and F plus Pb groups were found to be significantly depressed compared with controls. Interestingly, the western blotting technique, but not the immunofluorescence results indicated greater depression in the Pb group than in either the F or the F+Pb group. Overall, these findings may be helpful to gain a better understanding of the mechanism underlying F and Pb combined neurotoxicity.
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Lead(II) tetrafluoroborate and hexafluorosilicate complexes with 2,2'-bipyridyl, 1,10-phenathroline and 2,2':6',2 ''-terpyridyl have been prepared from the ligand and lead salt in aqueous/MeCN. Crystal structures are reported for [Pb(bipy)(2)(SiF6)], [Pb(phen)(2)(SiF6)] and [Pb(bipy)(2)(BF4)(2)] which are dinuclear with each lead coordinated "cis" to the two diimines and with the bridging fluoroanions completing eight or nine-coordination. [Pb(phen)(2)(BF4)(2)] is eight-coordinate and mononuclear with "cis" diimines and two kappa(2)-BF4- Z groups. [Pb(phen)(2)(H2O)(2)(SiF6)] is also mononuclear with a kappa(2)-SiF62- group and two coordinated water molecules. Reaction of Pb(BF4)(2) with 2,2':6',2 ''-terpyridyl gave only [Pb(terpy)(3)][BF4](2), but Pb(SiF6) produced [Pb(terpy)(H2O)(SiF6)], which is a chain polymer with bridging SiF62- groups and significant pi-stacking of the imine rings. The work has identified a number of coordination modes of the SiF62- anion, which has been little used in coordination chemistry but proves to be versatile and also stable (to decomposition/hydrolysis). (C) 2014 The Authors. Published by Elsevier Ltd.
Lead, cadmium, and fluoride were determined in 68 samples of market milk and about 115 infant formulas. Mean and median levels (ranges) in ng/g found for cow milk were as follows: lead, 1.12, 1.19 (0.01-2.48); cadmium, 0.10, 0.039 (0.005-0.74); and fluoride, 41, 40 (7-86). In canned, ready-to-use formulas, lead, cadmium, and fluoride levels averaged 37.3,1.50, and 840 ng/g, respectively. In concentrated liquid formulas, the respective levels were 21, 3.54, and 600 ng/g. In powder formula concentrates, respective levels were 73.7, 6.78, and 1130 ng/g. On the basis of this study and literature data, lead levels in market milk exceeding 5 ng/g appeared to signify contamination of the milk either directly or via the cow. For formulas considered on an as-consumed basis, lead levels exceeding about 10-15 ng/g were attributed to contamination from either the can used to store the formula or the formula ingredients. Infant formulas in lead-free cans contained about 1.7 ng/g of lead on a ready-to-use basis. Milkbased formulas contained about 0.26 ng/g of cadmium on a readyto- use basis. Soy-based or milk-free formulas contained about 8-15 times more cadmium than did milk-based formulas. Canadian and U.S. ready-to-use formulas contained 900 and 230 ng/g fluoride, respectively, and this difference was attributed to the level of fluoride in the processing water used by the manufacturers.
Article
Phosphate dosing of drinking water supplies, coupled with leakage from distribution networks, represents a significant input of phosphorus to the environment. The oxygen isotope composition of phosphate (δ18OPO4), a novel stable isotope tracer for phosphorus, offers new opportunities to understand the importance of phosphorus derived from sources such as drinking water. We report the first assessment of δ18OPO4 within drinking water supplies. Forty samples from phosphate-dosed distribution networks were analysed from across England and Wales. In addition, samples of the source orthophosphoric acid used for dosing were also analysed. Two distinct isotopic signatures for drinking water were identified (average = +13.2‰ or +19.7‰), primarily determined by δ18OPO4 of the source acid (average = +12.4‰ or +19.7‰). Depending on the source acid used, drinking water δ18OPO4 appears isotopically distinct from a number of other phosphorus sources. Isotopic offsets from the source acid ranging from -0.9‰ to +2.8‰ were observed. There was little evidence that equilibrium isotope fractionation dominated within the networks, with offsets from temperature-dependent equilibrium ranging from -4.8‰ to +4.2‰. Whilst partial equilibrium fractionation may have occurred, kinetic effects associated with microbial uptake of phosphorus or abiotic sorption and dissolution reactions may also contribute to δ18OPO4 within drinking water supplies.