in the matter - epa · 2019-04-06 · 2013). the main occurrences of uranium minerals in new...

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BEFORE THE EPA CHATHAM ROCK PHOSPHATE MARINE CONSENT APPLICATION IN THE MATTER of the Exclusive Economic Zone and Continental Shelf

(Environmental Effects) Act 2012 AND IN THE MATTER of a decision-making committee appointed to consider a

marine consent application made by Chatham Rock Phosphate Limited to undertake rock phosphate extraction on the Chatham Rise

__________________________________________________________

STATEMENT OF EVIDENCE OF DR DAVID BULL FOR

CHATHAM ROCK PHOSPHATE LIMITED

Dated: 28 August 2014

__________________________________________________________

__________________________________________________________

Barristers & Solicitors

J G A Winchester / H P Harwood Telephone: +64-4-499 4599

Facsimile: +64-4-472 6986

Email: [email protected]

DX SX11174 P O Box 2402 Wellington

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CONTENTS

EXECUTIVE SUMMARY ......................................................................................... 4

INTRODUCTION ...................................................................................................... 4

Qualifications and experience ......................................................................... 4

Code of conduct ................................................................................................ 6

Scope of evidence ............................................................................................. 6

URANIUM ................................................................................................................. 7

URANIUM IN PHOSPHORITE ................................................................................ 8

Chatham Rise phosphorite ............................................................................... 8

Comparison with other New Zealand sources ............................................... 9

URANIUM IN PHOSPHATE FERTILISERS ............................................................ 10

URANIUM ACCUMULATION IN FERTILISED SOILS ........................................... 11

Uranium immobile in soils ................................................................................ 11

Uranium not removed from soils ..................................................................... 12

Uranium accumulation in New Zealand soils ................................................. 13

RATE OF URANIUM ACCUMULATION ................................................................. 14

A SOIL GUIDELINE VALUE FOR URANIUM: HEALTH EFFECTS ...................... 16

Rural residents .................................................................................................. 16

Food chain considerations ............................................................................... 18

Soil guideline overview ..................................................................................... 20

SOIL GUIDELINE VALUES FOR URANIUM: ENVIRONMENTAL EFFECTS ...... 21

RESPONSES TO EPA STAFF REPORT ................................................................ 23

Phosphorus pentoxide ..................................................................................... 23

Tolerable daily intake of uranium .................................................................... 24

Uranium leaching from arable soils ................................................................ 25

SUMMARY ............................................................................................................... 26

REFERENCES ......................................................................................................... 27

APPENDIX 1 ............................................................................................................ 30

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APPENDIX 2 ............................................................................................................ 32

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EXECUTIVE SUMMARY

1. I have been asked to provide expert opinion of the potential for uranium

accumulation in New Zealand soils from the use of Chatham Rise rock

phosphate as a component to manufactured fertilisers such as super

phosphate and also as a direct application fertiliser.

2. Uranium is chemically toxic in elevated concentrations, and accumulates

slowly in fertilised soils. In my opinion, the probable rate of uranium

accumulation is slow; adverse chemical effects are unlikely to occur for at

least 100 years under current practices.

INTRODUCTION

Qualifications and experience 3. My full name is David Charles Bull.

4. I hold the degrees of Doctor of Philosophy in Environmental Science and

Bachelor of Science with Honours (first class) in Chemistry from the

University of Canterbury, as well as a Postgraduate Diploma in Science in

Environmental Science from the same institution.

5. I am a Senior Environmental Consultant in the Site Investigation,

Remediation and Auditing team at Golder Associates (NZ) Limited

(‘Golder’).

6. My principal role is to investigate, assess and advise on management of

contaminated sites for Golder clients. I have particular interests in the

distribution, speciation and bioavailability of contaminants, and in

quantitative risk assessment of contaminated land.

7. I have approximately 18 years of professional experience. In 2007 I was

awarded Chartered Chemist status by the Royal Society of Chemistry in

the United Kingdom, and Chartered Scientist status by the Science

Council in the United Kingdom. I am a member of the Royal Society of

Chemistry, the New Zealand Institute of Chemistry, and the New Zealand

Trace Elements Group. I have worked as a contaminated land expert for

the majority of my career, having been employed in this capacity with

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Golder, URS New Zealand Ltd and Entec UK Ltd. I also served for three

years as a Senior Researcher in the Parliamentary Commissioner for the

Environment’s office.

8. I have also held post-doctoral fellowships at the National Institute of Water

and Atmospheric Research (NIWA), Hamilton, and at the Georgia Institute

of Technology, Atlanta, both focusing on trace element chemistry in

sediments, and in particular reduction-oxidation chemistry, an

understanding of which is crucial to understanding trace element

speciation and mobility.

9. I have investigated and assessed numerous sites affected by potentially

toxic trace element contamination in New Zealand and the United

Kingdom, including antimony, arsenic, cadmium, chromium, copper, lead,

mercury, radium and thallium from defense sources, electroplating works,

fertiliser works, gasworks, mining, motorways, orchards, paint manufacture

and paint removal, railways, sheep dips, and timber treatment, at

agricultural, residential, commercial and industrial sites. Based on this

experience, I was seconded to the Parliamentary Commissioner to the

Environment’s office to provide technical expertise to her investigation of

the remediation of the contaminated site at Mapua.

10. At Golder I undertake site-specific contaminated land health risk

assessments. Over 2012-2013, I undertook the health risk assessment of

the Moanataiari subdivision in Thames. This unique assessment included

an investigation into the bioavailability of arsenic and lead, and derivation

of a soil guideline value for the rare trace element thallium, for which no

soil contaminant standards exist in New Zealand.

11. Further, I am familiar with issues around fertiliser application in New

Zealand farming, from my experience as lead researcher in the

Parliamentary Commissioner for the Environment's investigations Change

in the high country and Water quality in New Zealand: understanding the

science – a project in which Dr. Mackay was also involved.

12. I am an author of one patent, eight publications in peer-reviewed journals,

five public reports, and numerous consultancy reports.

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Code of Conduct

13. I confirm that I have read the Code of Conduct for expert witnesses

contained in the Environment Court of New Zealand Practice Note 2011

and that I have complied with it when preparing my evidence. Other than

when I state that I am relying on the advice of another person, this

evidence is entirely within my area of expertise. I have not omitted to

consider material facts known to me that might alter or detract from the

opinions that I express.

Scope of evidence

14. I have been asked to provide expert opinion of the potential for uranium

accumulation in New Zealand soils from the use of Chatham Rise rock

phosphate as a component to manufactured fertilisers such as super

phosphate and also as a direct application fertiliser.

15. I have also been asked to provide expert opinion on the potential for

adverse effects on the environment (including public health) due to

uranium accumulation in fertilised New Zealand soils, should it occur. My

evidence does not include any consideration of any potential occupational

health and safety risks associated with uranium in phosphate fertilisers.

16. There is little New Zealand-specific information on the potential effects of

uranium on health and the environment. Therefore, throughout my

evidence, I place particular reliance on six international reviews that I

consider to be generally authoritative, reflecting expert committee reviews

of published literature on uranium with agency consensus:

Toxicological profile for uranium, Agency for Toxic Substances and

Disease Registry (ATSDR), United States Department of Health and

Human Services. 2013.

Uranium in foodstuffs, in particular mineral water. Scientific opinion of

the Panel on Contaminants in the Food Chain. Updated version.

European Food Safety Authority (EFSA). May 2009.

Canadian soil quality guidelines for uranium: environmental and

human health. Scientific supporting document. Canadian Council of

Ministers for the Environment (CCME). 2007.

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Uranium-238 in the 2001 Total Diet Study. Food safety information

sheet FSIS 56/04. (United Kingdom) Food Safety Agency (UKFSA).

2005.

Uranium. Guidelines for Canadian drinking water quality: supporting

documentation (revised edition). Health Canada. 2001.

Depleted uranium: sources, exposure and health effects. World

Health Organisation (WHO). 2001.

17. Finally, I have been asked to address three matters raised by the EPA

staff report:

Whether diphosphorus pentoxide (P2O5) in Chatham Rise phosphorite

poses a hazard on handling and storage,

Whether the tolerable daily intake for uranium established by the

World Health Organisation is a preliminary guidance value only, and

Whether the use of phosphate fertilisers can be expected to lead to

uranium exceeding drinking water guidelines in groundwater.

URANIUM

18. Uranium is a trace element found in small quantities almost everywhere

within the natural environment, including rocks, soils, water, air, plants,

animals and all human beings (WHO 2001). Typical background

concentrations of uranium in soil and rock are around 2 mg/kg

(Golder 2014), making uranium roughly as common as tin. Uranium is

naturally more abundant than cadmium, another trace element associated

with phosphate fertilisers, which has a mean natural background

concentration of around 0.15 mg/kg (CRC 2005).

19. Natural uranium levels in New Zealand soils are poorly characterised.

Measured background uranium concentrations in New Zealand soils are

generally in the range 0.5-2.1 mg/kg (WRC 2011, Guinto 2011, McDowell

2013). The main occurrences of uranium minerals in New Zealand are

sandstone type deposits in the lower Buller Gorge and Pororari River

areas. Detrital uranium in the form of uraninite has been found at

Taramakau River and Gillespies Beach in Westland (Christie & Braithwaite

1999).

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20. Uranium naturally occurs at higher concentrations in some rocks and soils.

For example, soils across much of the western United States naturally

exceed 3 mg/kg uranium. Some granites and volcanic rocks contain 10-

20 mg/kg. Phosphorite deposits can reach 100-300 mg/kg with individual

samples as high as 900 mg/kg (Golder 2014).

21. Uranium is a non-essential element; it has no recognised role in the

metabolic cycles of plants or animals. Like many other non-essential trace

elements, uranium exhibits chemical toxicity to humans, plants and

animals at established levels of intake or exposure. These threshold

concentrations have been established by reputable scientific agencies

such as ATSDR, EFSA, Health Canada and WHO.

22. Phosphate fertilisers are a major source of uranium in the environment.

Globally, coal-fired power stations and uranium mining are also major

anthropogenic sources (ATSDR 2013, CCME 2007, EFSA 2009, WHO

2001).

23. Many New Zealanders would associate uranium with the nuclear industry

and with radioactivity. Nonetheless, uranium is an element present

throughout the environment, and in soils it principally poses a chemical

hazard rather than a radiological hazard (ATSDR 2013, CCME 2007).

Accordingly, my evidence covers only the chemical properties of uranium.

Radiological matters are covered in the evidence of Dr. Hermanspahn.

URANIUM IN PHOSPHORITE

Chatham Rise phosphorite

24. Phosphate fertilisers may contain uranium because uranium is often

enriched in the parent phosphorite rock. Uranium can accumulate in

phosphorites from marine sources because uranyl ion from seawater can

substitute into the crystal structure of apatites, the principal minerals in

phosphorites. Depending on their origin, phosphate minerals may also

contain varying amounts of other trace elements, notably cadmium

(Golder 2014)

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25. As a general rule, the amount of uranium in a phosphorite mineral

depends on its geological age. Younger deposits contain more uranium

(Baturin & Kochenov 2001). Chatham Rise phosphorite nodules are

relatively young, less than 10 million years old (Miocene-Pliocene:

Hughes-Allan 2011) and therefore have relatively high concentrations of

uranium.

26. There are 186 analyses of uranium in Chatham Rise phosphorite samples,

obtained from seven different research cruises. In samples representative

of the material to be mined by Chatham Rock Phosphate, the uranium

content ranged from 27-524 mg/kg (Golder 2014).

27. In practice, phosphorite rock mined from the Chatham Rise would be well

mixed. As described in the evidence of Mr van Raalte, phosphorite will be

mined in blocks, some 10 km2

at a time. The mining vessel will transport

loads on the order of 50,000 tonnes to port from the Chatham Rise. The

nodules would be mixed during mining and again during processing,

offloading and storage. Therefore the arithmetic mean concentration of

uranium is the primary parameter of interest in assessing application of

fertiliser to land.

28. The arithmetic mean uranium concentration in mined Chatham Rise

phosphorite material is approximately 155 mg/kg (Golder 2014).

Comparison with other New Zealand sources

29. Historically, New Zealand’s rock phosphate supplies came principally from

two Pacific Island sources, Nauru and Christmas Island. Some supplies

also came from North Africa and from the United States, especially during

World War II (NZIC 1999). A recent Fertiliser Association of New Zealand

publication states that Nauru phosphate contained 54-64 mg/kg uranium,

and Christmas Island phosphate contained 15-25 mg/kg (FANZ 2014).

Another published source reports that Nauru phosphate contains

64-121 mg/kg uranium and Christmas Island phosphate contains 31-56

mg/kg (see Taylor 2007).

30. Since the mid-1990s, New Zealand’s rock phosphate supplies have

principally come from North Africa, especially Morocco (NZIC 1999, FANZ

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2014). Concentrations of uranium in Moroccan phosphate are reported to

fall in the range 76-136 mg/kg (FANZ 2014) although the same source has

“North African” sources at 45-75 mg/kg (FANZ 2014).

31. CRP has recently analysed a number of commercially available fertilisers,

and found uranium concentrations of 20-91 mg/kg in 9 phosphate rock

samples, with an average of 66 mg/kg (Golder 2014).

32. By comparison, Chatham Rise phosphorite contains up to 2.5 times more

uranium than New Zealand’s current sources.

URANIUM IN PHOSPHATE FERTILISERS

33. Dr. Mackay’s evidence shows that Chatham Rise phosphorite could

beneficially be used directly as a fertiliser.

34. Alternatively Chatham Rise phosphorite could be processed into

‘superphosphate’ fertiliser. ‘Superphosphate’ is a product derived from

phosphorite that has been ‘acidulated’ with sulphuric acid and then

granulated into a spreadable form (NZIC 1998, 1999). The acidulation

process, as carried out in New Zealand, improves the fertiliser properties

by adding sulfur, increasing the solubility of the phosphate, and removing

fluoride (NZIC 1998, 1999).

35. Chatham Rise phosphorite can be made into high grade superphosphate

only as a blend with other rock. CRP’s research has identified that New

Zealand farmers demand high phosphorus content in their

superphosphate fertiliser. Chatham Rise phosphorite contains an average

of approximately 9.3% phosphorus by weight, which is a medium level

compared with overseas phosphorites. Unless the expectations of New

Zealand farmers change, Chatham Rise phosphorite would need to be

blended with a high grade phosphorite at a ratio of no more than

25 %:75 %, in order to make a superphosphate product that is marketable

in New Zealand.

36. A blend of phosphorites for superphosphate production would have a

lower uranium level than Chatham Rise phosphorite alone. Assuming

rather conservatively that Chatham Rise phosphorite (9.3% phosphorus,

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155 mg/kg uranium) was blended at 25 %:75 % with Moroccan high grade

phosphorite containing an average of 15 % phosphorus and 136 mg/kg

uranium (the upper end of the range in FANZ 2014), overall the raw

material would contain 13.6 % phosphorus and 141 mg/kg uranium.

37. Because the New Zealand acidulation process adds a weight of sulphuric

acid to the raw phosphorite, both the phosphorus and uranium

concentrations are diluted in the resulting superphosphate product, to

approximately 60% of their original levels. However, no phosphorus or

uranium is actually lost, so the phosphorus:uranium ratio does not change.

38. In principle, other manufacturing processes could also be used. In some

other countries, where it is less important that phosphate fertilisers contain

sulfur, calcium sulfate is removed from the superphosphate as a waste

material known as ‘phosphogypsum’. Removing phosphogypsum would

also remove some of the uranium (and its daughter products radium and

radon) from the product fertiliser. Further treatment yields products such

as ‘triple superphosphate’ or ammonium phosphate.

URANIUM ACCUMULATION IN FERTILISED SOILS

Uranium immobile in soils

39. In this part of my evidence I will show that uranium applied in fertilisers will

remain in the soil, and therefore accumulate in soils and soil-derived

sediments.

40. The environmental chemistry of many trace elements depends on the

environment in which they are found. Key factors are the acidity or

alkalinity of the medium, its oxidising or reducing potential, the presence of

minerals and organic matter. A trace element is mobile, and therefore

leachable, if it dissolves readily and is not adsorbed onto solid phase

materials. A trace element is immobile if it forms insoluble compounds or

if it is strongly adsorbed onto solid phases. As a first approximation, a

trace element in an immobile form is less bioaccessible for uptake by

plants and animals.

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41. Uranium is immobile in most soils (Golder 2014):

In reducing conditions, insoluble UO2 forms.

In oxidising, acidic conditions, soluble uranyl cation is dominant, but

readily adsorbs to common binding phases such as organic matter,

clays, iron and manganese oxides (except in strongly acid conditions,

or in the presence of certain chelating molecules, such as citric acid).

In oxidising, neutral conditions, the uranyl cation forms insoluble

hydroxide complexes.

In oxidising, alkaline conditions where carbonate concentrations are

high relative to phosphate, moderately soluble and mobile uranyl

carbonate complexes form.

42. Overall, it is my opinion that uranium is immobile in most New Zealand

fertilised soils:

Firstly, while uranium might be mobile in strongly acid soils with pH <5,

Dr. Mackay advises me that few New Zealand agricultural soils have

pH <5.5, and pH <5.0 would generally be avoided (by adding lime,

which raises pH) since aluminium and manganese become toxic to

plants in such acidic conditions.

Secondly, uranium is mobile in carbonate-rich alkaline soils, but Dr.

Mackay advises me that we have no such soils in agricultural use.

Thirdly, while uranium might also be mobile in sandy or stony soils with

few uranium binding phases, Dr. Mackay further advises me that such

soils are classed as high risk for phosphorus loss in overland flow

(along with podzols, peats and pallic soils), and hence phosphorus

fertiliser application would be avoided to protect water quality.

Uranium not removed from soils

43. Since uranium is expected to be immobile in most New Zealand fertilised

soils, losses through leaching are considered to be small.

44. Losses through runoff should also be small: runoff could carry away

uranium entrained in soil and fertiliser particles, but modern farming

practices actively minimise such losses, since this process moves valuable

fertiliser from the paddock to the waterway where it is environmentally

undesirable (PCE 2012).

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45. Plants do not readily remove uranium from soil. Except in highly

contaminated soils (CCME 2007), only plant roots have been observed to

hold appreciable quantities of uranium. Even for roots, the majority of the

uranium loading appears to be in and on the outer membrane of the root,

and not inside the plant (ATSDR 2013). Consequently, by one estimate,

wheat cropping might remove 6 g/ha/yr of uranium from soil (BfR

undated). There are no known terrestrial plants that are

hyperaccumulators of uranium (Ebbs et al. 1998).

46. Furthermore, animals do not readily take up uranium from soil following

ingestion. Investigations of humans and laboratory test animals show that

even the most soluble forms of uranium are poorly absorbed through the

skin, lungs, or gastrointestinal tract (bioavailability up to 6 %: ATSDR

2013). Uptake of insoluble forms of uranium, such as those generally

found in soils, is lower still (as little as 0.1 %: ATSDR 2013). Most of the

uranium that is absorbed is promptly excreted in urine.

47. Since phosphate fertilisers contain uranium that is immobile in soil, and

uranium is not readily removed from soil by plants or animals, it follows

that uranium accumulates in fertilised soils.

Uranium accumulation in New Zealand soils

48. Two regional studies confirm that uranium has generally accumulated in

fertilised soils:

In the Waikato, horticultural and arable soils were reported to average

2.4 mg/kg uranium, and pastoral soils average 1.8 mg/kg; in both

cases indicating accumulation above a natural background of

1.1 mg/kg, which was ascribed to fertilisers (WRC 2011).

In the Bay of Plenty, soil samples from dairy land were reported to

average 1.5 mg/kg uranium, kiwifruit (often former dairy land) 1.3

mg/kg, maize 1.1 mg/kg, sheep/beef 0.8 mg/kg, all above natural

background of 0.5 mg/kg (Guinto 2011, 2012).

I will discuss some studies of specific sites in the next section of my

evidence.

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49. Although uranium from fertilisers has accumulated in Waikato farmed soils

(WRC 2011), uranium is not enriched in Waikato lake sediments (WRC

undated), providing further empirical evidence that applied uranium has

remained immobile in Waikato soils.

RATE OF URANIUM ACCUMULATION

50. Having established that uranium generally accumulates in farmed soils, I

now turn to the rate of accumulation. As I have not identified any

significant uranium removal processes, uranium accumulation should be

the product of the uranium concentration in phosphate fertiliser, and the

rate of fertiliser application. The resulting concentration of uranium in soil

depends on the depth of fertiliser incorporation into the soil.

51. Phosphate fertiliser application rates are based on phosphorus content, as

mentioned previously: therefore, in New Zealand uranium accumulation

should be the same whether the phosphorite is applied as raw rock or

whether it is processed into superphosphate.

52. Dr. Mackay’s evidence states that phosphate fertilisers could be applied at

up to 40 kg P/ha/yr on dairy and horticultural land in the future.

Application rates for sheep/beef or arable farming would usually be rather

less, typically 10 kg P/ha, and for orcharding or viticulture less again.

53. In current New Zealand practice, intensively farmed land would generally

receive high grade superphosphate. As Dr. Mackay has stated in his

evidence, extensively farmed land is increasingly likely to receive raw

phosphorite, for environmental and agronomic reasons.

54. At paragraph 36 of my evidence, I showed that New Zealand high grade

superphosphate could contain up to 25 % Chatham Rise phosphorite in

future, therefore approximately 13.6 % phosphorus and 141 mg/kg

uranium. An application rate of 40 kg P/ha/yr therefore equates to

294 kg/ha/yr of blended and processed phosphorite, and 41 g/ha/yr of

uranium.

55. In his evidence, Dr Mackay states that applied uranium is likely to be

mixed through the top 7.5 cm of topsoil due to the action of earthworms

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and other soil biota. Conservatively assuming that 100 % of the applied

uranium remains in the top 7.5 cm of topsoil, then a maximum application

rate of 41 g/ha/yr of uranium would mean a maximum soil accumulation

rate of approximately 0.07 mg/kg/yr.

56. According to Dr. Mackay’s evidence, a more realistic uranium application

rate for ‘extensive’ farming, such as hill country sheep and beef, would be

approximately 10 kg P/ha/yr. Again conservatively assuming that 100 %

of the applied uranium remains in the top 7.5 cm of topsoil, this would

result in a soil uranium accumulation rate of approximately 0.03 mg/kg/yr.

57. By way of comparison, I am aware of four studies of historic uranium

accumulation on specific New Zealand farms:

Rothbaum et al. (1979) found uranium accumulating at approximately

0.026 mg/kg/yr on a pastoral farm at Papatoetoe between 1954 and

1975.

Taylor (2007) found uranium accumulating at 0.015-0.047 mg/kg/yr on

four North Island dairy farms between circa 1950 and 1992.

McDowell et al. (2012) found uranium accumulating at 0.006-0.009

mg/kg/yr at Winchmore sheep/beef research station, Canterbury,

between 1958 and 2005.

Schipper et al. (2011) found uranium accumulating at 0.019-0.067

mg/kg/yr at the Whatawhata hill country research farm near Hamilton

between 1983 and 2006. The highest rate relates to a block receiving

100 kg P/ha/yr: Dr. Mackay’s evidence shows that this is a much

higher application rate than would be anticipated in the future,

especially for a hill country farm.

58. In summary, if Chatham Rise phosphorite was incorporated into current

New Zealand farming practice, then uranium accumulation rates in areas

with extensive farming would be around 0.03 mg/kg/yr, within the range of

rates observed historically. In intensive farming scenarios, uranium

accumulation rates could be higher, up to 0.07 mg/kg/yr.

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A SOIL GUIDELINE VALUE FOR URANIUM: HEALTH EFFECTS

Rural residents

59. Having established that uranium will accumulate in agricultural soils

fertilised with Chatham Rise phosphorite, I now turn to the consequences

of accumulation. I first consider whether uranium concentrations in farmed

soils could affect the health of people living on the land, and then consider

whether it could have undesirable effects on public health through the food

chain.

60. New Zealand does not have a soil guideline value for uranium. However,

it has a regulatory methodology for calculating Soil Contaminant

Standards protective of people living in rural dwellings (MfE 2011a,b).

These Soil Contaminant Standards are incorporated by reference in the

Resource Management (National Environmental Standard for Assessing

and Managing Contaminants in Soil to Protect Human Health)

Regulations, which came into force on 1 January 2012.

61. The relevant exposure scenario is based on a small child, approximately

two years old, who lives almost all year on a lifestyle block. The child

accidentally ingests small quantities of soil in dirt and dust; eats

vegetables grown near the house, and soil adhering to those vegetables;

and is also exposed to contaminants when touching soil. Inhalation of fine

dust particles is implicitly but not explicitly included; this exposure pathway

is believed to contribute very little to overall exposure, and is difficult to

model accurately (MfE 2011b).

62. I have used this methodology to derive a soil guideline value for uranium.

The calculation requires certain element-specific input parameters:

A tolerable daily intake for uranium of 0.6 µg per kg body weight per

day (Health Canada 2001). This value is derived from a study in which

rabbits were fed highly soluble uranium compounds, and in which the

most sensitive end point observed was an effect on the kidney

(nephrotoxicity). A safety factor of 10 was applied for interspecies

uncertainty, and a further safety factor of 10 was applied for

intraspecies uncertainty. This value is inherently conservative when

considering exposure to uranium in soil, which is generally less soluble

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(Golder 2014) and therefore expected to be less bioavailable when

ingested. Health Canada considered an additional safety factor to

allow for the duration of the rabbit study (as ATSDR (2013) did) but

rejected this because nephrotoxicity occurred well within the study

timeframe, and did not affect animal survival. WHO recently proposed

a similar tolerable daily intake, 0.86 µg/kg/day, based on a small study

of human drinking water exposure in Finland (WHO 2011). This value

may be preferable as it is based on human data and reduces

extrapolation uncertainties.

A background dietary intake of uranium for New Zealand toddlers at

1.3 μg/day, identical to the estimate for Canadian children by CCME

(2007). I will describe this estimate in more detail in the next part of

my evidence (paragraphs 67-73 below).

Bioconcentration factors of 0.01 for uptake of soil uranium into root,

tuber and leafy vegetables (on a dry weight basis), based on data from

the background dietary intake assessment, and on my conservative

assumption of a background level of 2 mg/kg of uranium in agricultural

soils (Golder 2014).

A dermal exposure factor of 0.004 (ATSDR 2013) based on a dermal

exposure study using hairless rats.

A default oral bioavailability value conservatively left at 100%, relative

to the uranium nitrate-spiked feed used in the rabbit study cited by

CCME (2007).

63. I am unaware of any exposure pathway that has not been included within

the MfE model that would be likely to contribute significantly to uranium

exposure in the identified scenario. In particular, when inhalation of

uranium in dust is explicitly modelled by other regulators, it appears to

make a very minor contribution to overall exposure in a residential context.

64. On this basis, I calculate a soil guideline value for uranium of 90 mg/kg for

the protection of those living on land receiving fertiliser applications.

Detailed equations and calculations are provided in Appendix 1 of my

evidence.

65. The derived soil guideline for uranium is greater than the equivalent

Canadian value of 23 mg/kg. This difference arises principally because, in

the Canadian methodology, no more than 20 % of the effective tolerable

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daily intake of a contaminant may come from a residential soil source.

The MfE methodology considers and rejects this approach: “Canada

[chooses] to assign only one-fifth of the acceptable daily intake of a

substance to the soil compartment. There is no scientific justification for

this, it is purely a policy decision” (MfE 2011b). In my view MfE may be

overstating its case, but the point is moot provided that exposure from all

significant sources is taken into account, as is done here.

Food chain considerations

66. I now turn to the wider issue of uranium in the diet as a result of fertiliser

application. We do not know what uranium levels in the New Zealand diet

may be, as uranium has never been included in the New Zealand Total

Diet Surveys carried out by ESR for the New Zealand Food Safety

Authority (a precursor of the Ministry of Primary Industries). Uranium was

not detected in any of 53 samples of potatoes and 36 samples of onions

purchased around the Waikato region in 2005 (detection limit 0.4 μg/kg

wet weight: WRC 2005).

67. International assessments indicate that typical dietary intakes of uranium

are on the order of 2-16% of tolerable daily intakes (ATSDR 2013, CCME

2007, UKFSA 2005, Anke et al. 2009, EFSA 2009). Bread, baked goods,

fruit and vegetables are the major contributors of uranium to dietary intake

(ATSDR 2013, CCME 2007, UKFSA 2005, Anke et al. 2009, EFSA 2009)

along with soil entrained on unwashed root vegetables (ATSDR 2013).

Among sampled foodstuffs, the highest uranium concentrations were

encountered in shellfish, offal, seaweed and mushrooms (refer also

Kuwahara et al 1997).

68. I note that none of these authorities consider uptake through milk to be

particularly significant. UKFSA (2005) and Anke et al. (2009) report

uranium at just 0.00002 mg/kg in British and German cows’ milk,

respectively.

69. All these assessments were conducted in developed countries that have

used phosphate fertilisers in agriculture for several decades. Detailed

data on soil uranium concentrations is not supplied in any of these dietary

studies, but I infer that uranium concentrations in soils where the foods

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were grown are likely to be above natural background, i.e. averaging at

least 2 mg/kg.

70. Given this information, I can form an estimate of the uranium content of

the New Zealand diet. Multiplying average daily food consumption rates

from the latest New Zealand Total Diet Survey (NZFSA 2009) by typical

food uranium concentrations from the latest United Kingdom Total Diet

Study (UKFSA 2005), I estimate that the average New Zealand child aged

1-3 consumes approximately 0.65 μg/day of uranium in food. I obtain the

same result if I instead use mean food uranium concentrations from

Germany (Anke et al. 2009). 0.65 μg/day is approximately one-twelfth of

the tolerable daily intake (Health Canada 2001).

71. I have found no data on uranium concentrations in New Zealand drinking

water supplies. For two regions where I have found data, the mean

drinking water uranium concentration in Ontario is 2 μg/L (CCME 2007),

and the mean uranium concentration in tap water from northern Germany

is also 2 μg/L (Schnug et al 2005). Using this concentration, and daily

drinking water consumption from the latest New Zealand Total Diet Survey

(NZFSA 2009), I estimate that the average New Zealand child aged 1-3

consumes approximately 0.65 μg/day of uranium in drinking water. This is

a further one-twelfth of the tolerable daily intake.

72. There is likely to be a linear relationship between uranium concentrations

in a specific soil and in food grown on that soil (ATSDR 2013, citing a

1984 study). That is, if uranium accumulation causes the concentration of

uranium in a soil to double, the concentration of uranium in produce from

that land is also expected to double.

73. Applying this linear relationship, and beginning with a typical background

concentration of 2 mg/kg uranium, I estimate that dietary uranium would

not exceed a toddler’s tolerable daily intake unless agricultural soils

contained approximately 20 mg/kg of uranium.

74. However, there are many uncertainties in this estimate.

The tolerable daily intake derived by CCME (2007) is an estimate

based on an animal study to which a 100-fold safety factor has been

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applied, along with other conservative elements, including an

assumption of 100% relative bioavailability. This is a standard

approach (refer MfE 2011a), and the value is supported by other

scientific agencies, one of whom also invokes a study of human

exposure in drinking water (WHO 2011).

No-one can rule out the possibility that future research may identify

more sensitive toxicological endpoints that would warrant setting a

lower tolerable daily intake.

Food consumption rates and food preferences vary significantly from

child to child.

Bioconcentration factors from soil to produce vary significantly from

soil to soil and between different kinds of produce.

The contribution from uranium in drinking water to dietary intake is an

estimate only, as there is no New Zealand data.

The linear relationship between soil concentrations and produce

concentrations does not hold at highly contaminated sites. Among

studies reviewed by CCME (2007), bioconcentration factors are

significantly higher in soils containing 30-600 mg/kg uranium (refer

Golder 2014).

75. Accordingly, on the information currently available to me, I consider that a

further uncertainty factor of 50% could appropriately be applied. That is, in

order to maintain food quality so that dietary intakes remain within

tolerable limits, I consider that it would be inadvisable for uranium in

agricultural soils to exceed an indicative threshold of 10 mg/kg, until

uncertainties can be reduced through further research by regulatory

agencies.

Soil guideline overview

76. Based on the current available information I have presented, it is my

opinion that uranium in fertilisers derived from Chatham Rise phosphorite

poses little chemical risk to rural residents.

77. However, I consider that accumulation of uranium in soil should be limited

in order to protect food quality. I propose an indicative threshold of

10 mg/kg, which includes an uncertainty factor of 50%.

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78. Even on this conservative basis, uranium in Chatham Rise phosphorite

appears to pose little risk to food quality:

If uranium accumulated at 0.07 mg/kg/yr in intensively farmed soils

receiving high grade superphosphate partly derived from Chatham

Rise phosphorite, then those soils would take more than 100 years to

move from a background of 2 mg/kg to exceed a threshold of

10 mg/kg.

If uranium accumulated at 0.03 mg/kg/yr in extensively farmed soils

only receiving Chatham Rise phosphorite, then those soils would not

exceed a threshold of 10 mg/kg for approximately 300 years.

79. This lengthy time frame gives ample opportunity for scientific studies

supporting the approach outlined above, for example incorporating

uranium into national surveys of fertiliser, soil, groundwater, and food.

Since uranium is present in existing phosphate fertilisers, such studies

would presumably be undertaken in any case.

SOIL GUIDELINE VALUES FOR URANIUM: ENVIRONMENTAL EFFECTS

80. Developing soil guideline values for protecting the environment is

considerably more difficult than calculating values protective of human

health, because there are so many different species requiring protection

and so many different potentially affected environments. There are no

environmental soil guideline values for uranium in New Zealand, and there

is no national methodology for developing such values. In this part of my

evidence, I will examine environmental guideline values for uranium from

other jurisdictions, and consider their application to New Zealand

agricultural land.

81. Canadian authorities have derived an environmental soil guideline value of

33 mg/kg to protect the health of grazing mammals (CCME 2007). This

value was based on a rabbit study, because rabbits were understood to

ingest a relatively large proportion of soil in their diet (up to 6 % by weight),

and were therefore considered to be at particular risk from soil uranium.

While rabbits are undesirable in New Zealand farming systems, New

Zealand cattle and sheep may also ingest large amounts of soil, especially

when wintered on paddocks (up to 2 % of diet by weight: Healy 1968) and

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I consider this environmental guideline value should be applied to them

too.

82. Canadian authorities have also derived an environmental soil guideline

value of 500 mg/kg for protection of soil biota including field mustards

(turnips and related crops), Canadian wheatgrass, and collembola (tiny,

ubiquitous soil-dwelling arthropods) (CCME 2007).

83. A recent literature review (Sheppard et al. 2005) suggests the following

values:

100 mg/kg protective of soil organisms including bacteria, earthworms

and invertebrates,

100 mg/kg in soil-derived sediment would also appear to be protective

of sediment biota,

250 mg/kg protective of land plants.

No environmental soil guideline value was suggested to protect birdlife

(whether wild or farmed), as birds appeared relatively insusceptible to

uranium toxicity (Sheppard et al. 2005).

84. I cannot rule out the possibility that New Zealand’s endemic birdlife may

be more susceptible than the bird species studied elsewhere. However,

the Canadian environmental soil guideline value for protection of grazing

mammals offers at least an order of magnitude safety factor.

85. In conclusion, I consider an appropriate environmental threshold for

uranium would be 30 mg/kg, being the Canadian environmental soil

guideline value for protection of grazing mammals, rounded down to one

significant figure. This value appears likely to protect the most sensitive

receptors identified, namely grazing stock. This value is less stringent

than the threshold soil guideline value of 10 mg/kg that I recommended to

protect food quality earlier in my evidence.

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RESPONSES TO EPA STAFF REPORT

Phosphorus pentoxide

86. At paragraph 157 of the EPA staff report, EPA states that phosphorus

from Chatham Rise phosphorite nodules and seabed sediments “…is

present in the form of diphosphorus pentoxide (P2O5), a hazardous

substance…” EPA returns to this theme at paragraphs 161 and 162,

“Diphosphorus pentoxide is a potent dehydrating agent that reacts

vigorously with water and water-containing substances… [is corrosive] to

metal, skin and eyes... toxic by inhalation… conditions to avoid when

handling P2O5 are excess heat, dust formation and exposure to air or

water… There is the potential for the generation of dust from phosphate

nodules and exposure of P2O5 to air and humans during the sorting and

packing process onboard… potential effects on human health are

uncertain at this time.” These alleged risks appear to be one reason why

EPA seeks a Vessel Operational Management Plan per proposed

Condition 21 “…to address operational matters, including those related to

worker health and safety, human health and effects on handling and

exposure to hazardous substances.”

87. The EPA appears to have misunderstood this issue and the science

behind it. As a consequence, the EPA staff report has completely

overstated both the effects and risks. The description of phosphorite

nodules as containing 19-24% P2O5 is purely by convention; the

phosphorus content is calculated and reported as if it were the oxide, in

order to enable comparison to other phosphorus-containing fertilisers. In

describing and calculating phosphorus content in this way, there is no

intention to imply that phosphorus is present in the chemical form

P2O5. As the EPA has noted, P2O5 reacts vigorously with water. As such,

P2O5 cannot possibly exist in the ocean or any other environment where

water is present. Phosphorus in phosphorite nodules is principally

present as apatites (calcium phosphates). Apatites are familiar minerals,

forming the inorganic component of bones and teeth.

88. The EPA is quite incorrect that the potential effects of phosphorite nodules

on human health are uncertain. Marine phosphorites have been used as

fertilisers in New Zealand since 1900 (NZIC 1998), and hundreds of

thousands of tonnes of marine phosphorite are handled, processed and

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applied to land every year (Statistics New Zealand 2012). As such, the

EPA and the Department of Labour have already assessed their potential

effects on health and the environment. Materials safety data sheets

(MSDS) for phosphorite (‘reactive phosphate rock’, ‘RPR’) are readily

available from major fertiliser companies (e.g. Ravensdown 2005). These

MSDS show that phosphorites are not classified as hazardous chemicals;

they may be handled, stored and transported by any person, are not

corrosive, have low toxicity and low irritant tendencies (Ravensdown

2005). In conditions where dusts may form, ventilation and/or personal

protection is recommended (Ravensdown 2005); however, as I

understand the process, phosphorite nodules will not be dried on board

and therefore there will be no dust formation on board.

89. I believe that the phosphate component of Chatham Rise phosphorite

poses a low to negligible occupational health and safety hazard. The

hazard is controlled through existing health and safety legislation and

regulations.

Tolerable daily intake of uranium

90. At paragraph 165, the EPA states that uranium “even at current levels in

drinking water that are regarded as being safe, could increase the risk of

fertility problems and reproductive cancers. This is why the Tolerable Daily

Intake (TDI) that the World Health Organization (WHO) provides, which

has been quoted by the CRP application, should only be used as a

preliminary guidance.” These claims are referenced to a German text,

‘The New Uranium Boom’, Merkel and Schipek, eds., Springer-Verlag,

Heidelberg, 2011.

91. Contrary to the view of the German authors, the tolerable daily intake (TDI)

provided by the WHO has considerable support from other regulatory

authorities in New Zealand and worldwide. At the time that The New

Uranium Boom was written, the WHO TDI was set at 0.6 μg soluble

uranium per kg of body weight per day (WHO 2004), which had been

accepted by the European Food Safety Authority (EFSA 2009), and the

Australian National Health and Medical Research Council (NHMRC 2013).

The 2004 TDI replaced an earlier derivation of 0.5 μg/kg/d (WHO 2001)

that had been accepted by the United Kingdom Food Safety Authority

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(UKFSA 2004). The 2004 TDI has subsequently been replaced by a value

of 0.86 μg/kg/d, based on a study of human drinking water exposure in

Finland (WHO 2011). Similar TDIs are derived by Health Canada

(0.6 μg/kg/d: Health Canada 2001) and the United States Agency for

Toxic Substances and Disease Control (0.2 μg/kg/d: ATSDR 2013). Of

these studies, WHO (2011) and ATSDR (2013) post-date Merkel and

Schipek and have had an opportunity to study the same information. The

New Zealand Ministry of Health implicitly recognises that the TDI of

uranium is in this range of 0.2-0.86 μg/kg/d, in that New Zealand’s drinking

water standard for uranium (0.02 mg/L: MoH 2005), is very similar to

drinking water standards for Australia (0.017 mg/L), Canada (0.02 mg/L),

the United States (0.03 mg/L), and the current World Health Organisation

recommendation (0.03 mg/L).

Uranium leaching from arable soils

92. Footnote 315 to paragraph 504 of the EPA staff report reads: “Note: As

recent research indicates leaching of uranium from arable soils and

presence of fertiliser-derived uranium in ground- and drinking water, it is

suggested that the uncontrolled loading of the toxic and radioactive heavy

metal to soils should be regulated by state authorities, as it is done for

cadmium” [referenced to ‘The New Uranium Boom’]

93. The research presented in ‘The New Uranium Boom’ indicates elevated

uranium concentrations in groundwaters underlying some loess soils of

northeastern Germany. These elevated concentrations are still below

German (and New Zealand) drinking water guidelines. Unlike New

Zealand agricultural soils, loess is rich in carbonate, poor in organic

material, and very highly draining. Since uranium leaching is enhanced by

carbonate, reduced by organic material, and enhanced by good soil

drainage, I would expect loess soils to be prone to uranium loss following

phosphate fertiliser application, unlike New Zealand agricultural

soils. Moreover, the fact that the resulting uranium concentrations remain

below drinking water guidelines indicates that uranium losses from

fertilised soils to groundwater are minor, even in those circumstances.

94. I note that elsewhere in Germany, mineral waters and tap waters sourced

from mineralized, forested catchments have substantially greater uranium

concentrations, occasionally exceeding German drinking water guidelines

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by considerable margins (‘The New Uranium Boom’, Anke et al. 2009,

Schnug 2012). These exceedances have nothing to do with phosphate

fertiliser use.

SUMMARY

95. Chatham Rise phosphorite contains more uranium than the Pacific rock

phosphates that New Zealand historically used for fertiliser.

96. Uranium exhibits chemical toxicity to humans, plants and animals at

established levels of intake or exposure, and accumulates slowly in

fertilised soils.

97. I consider it likely that Chatham Rise phosphorite, whether raw or

processed, could be applied to intensive farming operations for 100 years

or more, before reaching a threshold of 10 mg/kg, which I consider

protective of the current tolerable daily intake established by Health

Canada (2001).

98. I consider that a uranium soil guideline value of 10 mg/kg for agricultural

soils would also be protective of less sensitive receptors, such as people

living on the land, stock, soil and sediment biota, and plant health.

David Bull

28 August 2014

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REFERENCES

Anke M, Seeber O, Muller R, Schafer U, Zerull J. Uranium transfer in the food chain

from soil to plants, animals and man. Chemie der Erde 69(S2): 75-90.

ATDSR 2013. Toxicological profile for uranium. Agency for Toxic Substances and

Disease Registry, United States Department of Health and Human Services. Atlanta,

Georgia, USA.

Baturin GN, Kochenov AV 2001. Uranium in phosphorites. Lithology and Mineral

Resources 36: 303-321.

BfR undated. BfR empfiehlt die Ableitung eines europäischen Höchstwertes für Uran in

Trink- und Mineralwasser. Bundesinstitut fur Risikobewertung (Federal Institute of Risk

Assessment). Germany.

CCME 2007. Canadian soil quality guidelines for uranium: environmental and human

health. Canadian Council of Ministers of the Environment Scientific Supporting

Document.

Christie T, Braithwaite B 1999. Mineral Commodity Report 19 – Beryllium, gallium,

lithium, magnesium, uranium and zirconium. New Zealand Mining 26: 27-42.

CRC 2005. Handbook of chemistry and physics. 85th edition. CRC Press, Boca Raton,

Florida.

Ebbs SD, Brady DJ, Kochian LV 1998. Role of uranium speciation in the uptake and

translocation of uranium by plants. Journal of Experimental Botany 49: 1183-1190.

EFSA 2009. Scientific opinion: uranium in foodstuffs, in particular mineral water.

Revised version dated 29 May 2009. The EFSA Journal 1018: 1-59. European Food

Safety Authority.

FANZ 2014. Uranium – in soil, plants and fertiliser. Fertiliser Association of New

Zealand Technical Paper. July 2014.

Golder 2014. Uranium in phosphorite. Report prepared by Golder Associates (NZ)

Limited for Chatham Rock Phosphate. August 2014. (attached as Appendix 2)

Guinto D 2011. Trace elements in Bay of Plenty soils. Bay of Plenty Regional Council,

Environmental Publication 2011/16.

Guinto DF 2012. Temporal changes in topsoil trace element concentrations in the Bay

of Plenty. Paper presented at the 25th annual Fertiliser and Lime Research Centre

workshop, Massey University, Palmerston North, New Zealand.

Health Canada 2001. Uranium. Revised and edited version. Guidelines for Canadian

drinking water quality.

Healy WB 1968. Ingestion of soil by dairy cows. New Zealand journal of agricultural

research 11(2): 487-499.

Hughes-Allan SLM 2011. Genesis of the Chatham Rise phosphorite: an interpretation

from current literature. Paper to Australian Institute of Minerals and Mining New

Zealand Branch Conference 2011.

Kuwahara C, Koyama K, Sugiyama H 1997. Estimation of daily uranium ingestion by

urban residents in Japan. Journal of radioanalytical and nuclear chemistry 220(2):

161-165.

McDowell RW 2012. The rate of accumulation of cadmium and uranium in a long-term

grazed pasture: implications for soil quality. New Zealand Journal of Agricultural

Research 55: 133-146.

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McDowell RW, Taylor MD, Stevenson BA 2013. Natural background and anthropogenic

contributions of cadmium to New Zealand soils. Agriculture, Ecosystems and

Environment 165: 80-87.

MfE 2011a. Toxicological intake values for priority contaminants in soil. Ministry for the

Environment. Wellington.

MfE 2011b. Methodology for deriving standards for contaminants in soil. Ministry for

the Environment. Wellington.

MoH 2005. Drinking water standards for New Zealand 2005. Ministry of

Health. Wellington.

NHMRC 2013. Australia drinking water guidelines 6: 2011. Version 2.0 updated

December 2013. National Health and Medical Research Council. Canberra, Australian

Capital Territory, Australia.

NZIC 1998. Chemical processes in New Zealand. 2nd

edition. New Zealand Institute of

Chemistry. Christchurch.

NZIC 1999. New Zealand is different. New Zealand Institute of Chemistry.

Christchurch.

NZFSA 2009. 2009 New Zealand total diet study: agricultural compound residues,

selected contaminant and nutrient elements. Institute of Environmental Science and

Research (ESR) for New Zealand Food Safety Authority. Ministry for Agriculture and

Forestry. Wellington.

PCE 2012. Water quality in New Zealand: understanding the science. Parliamentary

Commissioner for the Environment. Wellington.

Ravensdown 2005. Reactive phosphate rock (RPR). Material safety data sheet.

Ravensdown Fertiliser Co-operative Limited. Napier.

Rothbaum HP, McGaveston DA, Wall T, Johnston AE, Mattingly GEG 1979. Uranium

accumulation in soils from long-continued applications of superphosphate. Journal of

Soil Science 30: 147-153.

Schipper LA, Sparling GP, Fisk LM, Dodd MB, Power IL, Littler RA 2011. Rates of

accumulation of cadmium and uranium in a New Zealand hill farm soil as a result of

long-term use of phosphate fertilizer. Agriculture, Ecosystems & Environment 144:

95-101.

Schnug E. 2012. Pest oder Cholera? – Uran aus Düngern über den Boden ins

Trinkwasser oder in Atomstrom? Strahlentelex 612-613: 3-10.

Sheppard SC, Sheppard MI, Gallerand MO, Sanipelli B 2005. Derivation of ecotoxicity

thresholds for uranium. Journal of Environmental Radioactivity 79(1): 55-83.

Statistics New Zealand 2012. 2012 agricultural census tables. Available on line at

www.stats.govt.nz.

Taylor M 2007. Accumulation of uranium in soils from impurities in phosphate fertilisers.

Landbauforschung Voelkenrode 2 57: 133-139.

UKFSA 2005. Uranium-238 in the 2001 total diet study. Food survey information sheet

FSIS 56/04. United Kingdom Food Safety Authority.

Welford & Baird 1967. Uranium levels in human diet and biological materials. Health

Physics 13: 1321-1324.

WHO 2001. Depleted uranium: sources, exposure and health effects. Department of

Protection of the Human Environment, World Health Organisation. Geneva.

http://www.stats.govt.nz/

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WHO 2004. Uranium in drinking-water. Background document for derivation of WHO

guidelines for drinking-water quality. Draft for consultation. World Health

Organisation. Geneva, Switzerland.

WHO 2011. Uranium in drinking-water. Background document for derivation of WHO

guidelines for drinking-water quality. World Health Organisation. Geneva, Switzerland.

WRC 2005. Cadmium accumulation in Waikato soils. Environment Waikato technical

report 2005/51. Waikato Regional Council. Hamilton.

WRC 2011. Summary statistics for trace elements in Waikato soils. Spreadsheet,

document 1946876v1. Waikato Regional Council. Hamilton. March 2011.

WRC undated. Regional lake sediments – update. Spreadsheet document 1975330v1.

Waikato Regional Council. Hamilton.

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APPENDIX 1: SOIL GUIDELINE VALUE FOR URANIUM - CALCULATION

In the following calculation, highlighting indicates parameters changed from generic values (MfE 2011b)

Site Generic Scenario Lifestyle block Receptor Child Contaminant Uranium Reference health standard RHS 0.0006 mg/kg bw/day Health Canada (2001) Background exposure BI 0.0001 mg/kg bw/day See Golder (2014). Food 0.00005 mg/kg bw/day, drinking water 0.00005 mg/kg bw/day. Based

on New Zealand Total Diet Study 2009, uranium concentrations for British (UKFSA 2005) or German (Anke et al. 2009) foods, and on mean uranium concentrations of 0.002 mg/L for Ontario drinking water (CCME 2007) and North German tap water (Schnug et al. 2005)

Effective RHS RHS 0.00050 mg/kg bw/day

RHS-BI

Body weight BW 13 kg bw Methodology for deriving standards for contaminants in soil, MfE 2011 Exposure frequency EF 350 day/year Methodology for deriving standards for contaminants in soil, MfE 2011 Bioavailability BA 100% Toxicological intake values for contaminants in soil, MfE 2011 Ingestion rate IR 50 mg soil/day Methodology for deriving standards for contaminants in soil, MfE 2011 SGVing 136 mg/kg soil

Home-grown produce consumption

Pg 25% Methodology for deriving standards for contaminants in soil, MfE 2011

Produce consumption IP 0.0105 kg veg/day Methodology for deriving standards for contaminants in soil, MfE 2011 Proportion roots proot 0.1 Bioconcentration factor - roots

BCFroot 0.01 See Golder (2014). UKFSA (2005) and Anke et al. (2009) uranium content in British and German carrots and onions, weighted average based on NZ Total Diet Survey intakes for 1-3 year-old, divided by 2 mg/kg assumed concentration in agricultural soils.

Soil loading - roots SLroot 0.001 g soil/g veg Methodology for deriving standards for contaminants in soil, MfE 2011

Proportion tubers ptuber 0.6 Methodology for deriving standards for contaminants in soil, MfE 2011 Bioconcentration factor - tubers

BCFtuber 0.01 See Golder (2014). UKFSA (2005) and Anke et al. (2009) uranium content in British and German potatoes, weighted average based on NZ Total Diet Survey intakes for 1-3 year-old, divided by 2 mg/kg assumed concentration in agricultural soils.

Soil loading - tubers SLtuber 0.001 g soil/g veg Methodology for deriving standards for contaminants in soil, MfE 2011

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Proportion leafy vegetables pleafy 0.3 Methodology for deriving standards for contaminants in soil, MfE 2011 Bioconcentration factor - leafy veg

BCFleafy 0.01 See separate calculation. UKFSA (2005) and Anke et al. (2009) uranium content in British and German vegetables, weighted average based on NZ Total Diet Survey intakes for 1-3 year-old, divided by 2 mg/kg assumed concentration in agricultural soils.

Soil loading - leafy vegetables

SLleafy 0.0002 g soil/g veg Methodology for deriving standards for contaminants in soil, MfE 2011

SGVp 240 mg/kg soil

Skin area AR 1900 cm2 Methodology for deriving standards for contaminants in soil, MfE 2011

Soil adherence factor AH 0.04 mg soil/cm2 Methodology for deriving standards for contaminants in soil, MfE 2011

Dermal absorption factor AF 0.004 ATSDR (2013) SGVd 22300 mg/kg soil

Particle emission factor PEF Inhalation rate IH 6.8 m

3/day Methodology for deriving standards for contaminants in soil, MfE 2011

Proportion retained in lungs R SGVih Incomplete mg/kg soil

Background concentration 2.1 mg/kg soil WRC (2011) 95th percentile of background dataset Combined soil guideline value

SGV 86 mg/kg soil Inverse of sum of inverses of pathway-specific SGVs

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APPENDIX 2: URANIUM IN PHOSPHORITE – REPORT PREPARED BY

GOLDER ASSOCIATES (NZ) LIMITED

August 2014


Report Number: 1178207517/Phase 017

Submitted to:Chatham Rock Phosphate LimitedPO Box 231Takaka


August 2014Report No. 1178207517/Phase 017 i

Table of Contents

1.0 INTRODUCTION ........................................................................................................................................................ 1

1.1 Background................................................................................................................................................... 1

1.2 Report Scope ................................................................................................................................................ 1

2.0 GEOLOGY AND GEOCHEMISTRY .......................................................................................................................... 2

2.1 General Geology ........................................................................................................................................... 2

2.2 Geochemistry................................................................................................................................................ 2

3.0 URANIUM IN PHOSPHORITE................................................................................................................................... 2

3.1 Phosphorite................................................................................................................................................... 2

3.2 Uranium in Chatham Rise Phosphorite ......................................................................................................... 4

4.0 URANIUM IN PHOSPHATE FERTILISERS .............................................................................................................. 8

4.1 Phosphorites used in New Zealand .............................................................................................................. 8

4.2 Processing Phosphorites into Fertilisers ....................................................................................................... 8

4.3 Uranium in Current New Zealand Fertilisers ................................................................................................. 8

5.0 BACKGROUND CONCENTRATIONS IN NEW ZEALAND SOILS .......................................................................... 9

6.0 ENVIRONMENTAL GUIDANCE................................................................................................................................ 9

7.0 ENVIRONMENTAL MOBILITY................................................................................................................................ 10

7.1 Accumulation of Uranium in Fertilised Soils ................................................................................................ 10

7.1.1 International studies .............................................................................................................................. 10

7.1.2 New Zealand studies ............................................................................................................................. 10

7.2 Mechanisms of Accumulation ..................................................................................................................... 11

7.3 Uranium Uptake .......................................................................................................................................... 12

7.3.1 Plants .................................................................................................................................................... 12

7.3.2 Animals ................................................................................................................................................. 13

7.4 Predicted Changes Associated with Phosphorite Application ..................................................................... 13

8.0 SUMMARY ............................................................................................................................................................... 13

9.0 LIMITATIONS .......................................................................................................................................................... 14

10.0 REFERENCES ......................................................................................................................................................... 14


August 2014Report No. 1178207517/Phase 017 ii

TABLES

Table 1: Uranium content of phosphorites by location. ....................................................................................................... 3

Table 2: Uranium content of phosphorite deposits by age of deposit (after Baturin & Kochenov 2001). ............................. 3

Table 3: Summary of U and P data in bulk samples from Chatham Rise surveys. ............................................................. 4

Table 4: Summary of U and P data in fine and coarse samples from the Dorado and Sonne cruises. ............................... 6

Table 6: Uranium background concentrations in New Zealand soils. .................................................................................. 9

Table 7: CCME (2007) soil quality guideline values for U in agricultural soils (all data mg/kg). .......................................... 9

FIGURES

Figure 1: Violin plot of uranium abundances in bulk samples from Chatham Rise surveys. Bulges in the outlines (violins) indicate greater numbers of samples. ................................................................................................... 5

Figure 2: Stacked distributions of uranium in samples collected from the Chatham Rise surveys. ..................................... 6

Figure 3: Histogram of U concentrations in phosphorite nodules from the Chatham Rise. ................................................. 7

Figure 4: Uranium in Waikato soils (from Taylor et al. 2011) (middle line = median, coloured box = upper and lower quarters, whiskers = 95 % confidence interval, dots = samples outside 95 % confidence interval). ....... 11

APPENDICES

APPENDIX AUranium in Chatham Rise Phosphorites: Raw Data

APPENDIX BChemical Analyses of Current Phosphate Fertilisers

APPENDIX CEstimates of Uranium Dietary Intake and BCFs

APPENDIX DReport Limitations


August 2014Report No. 1178207517/Phase 017 1

1.0 INTRODUCTION

1.1 Background Chatham Rock Phosphate Limited (CRP) holds a mineral prospecting licence (MPL 50270) for an area of the Chatham Rise. CRP has recently applied for a marine consent covering MPL 50270 and a proposed prospecting permit area located to the west of MPL 50270. The proposed marine consent covers an area of 5,207 km

2 some 450 km east of Christchurch. CRP proposes to initially mine phosphorite within a sub-area

of approximately 820 km2 of MPL 50270, at depths of 350 to 450 m.

Phosphorite, often known as rock phosphate, is a raw material for manufactured phosphate fertilisers. The Chatham Rise deposit is the largest known phosphorite deposit in the New Zealand Exclusive Economic Zone. Although the resource has been known for more than 60 years and has been the subject of ongoing prospecting, it has never been mined.

The trace element content of phosphorites varies depending on the geographic location of the deposit. Chatham Rise phosphorite has been found to contain less cadmium than the Moroccan phosphorite. Lower cadmium fertilisers are of interest because of concerns over cadmium accumulation in some intensively-farmed areas of New Zealand (TRC 2005, WaiRC 2005, MAF 2008, MPI 2011, MPI 2012).

However, on the Chatham Rise the paleo-environment during nodule formation led to increased concentrations of uranium (U) in the nodules relative to some other deposits. Uranium is a potentially toxic element, so its mobility in soils and its potential effects on plants and animals must be considered if the phosphorites mined by CRP are incorporated into fertiliser.

1.2 Report Scope This report has been prepared by Golder Associates (NZ) Limited for CRP to summarise what is known about uranium in phosphorite nodules from the Chatham Rise, and the implications of the use of phosphorite as fertiliser in New Zealand. The report presents the following:

An overview of U geochemistry.

A review of U in phosphorite from the Chatham Rise, and a comparison with the U content of other fertilisers.

An overview of U in New Zealand soils and a summary of the behaviour of U in New Zealand soils.

For the purposes of this assessment, it has been assumed that phosphorite mined from the Chatham Rise will not be blended with other fertilisers. In other words, it has been assumed that phosphorite will be sold,

Chatham Rise phosphorite has been demonstrated to be effective as a direct application phosphate fertiliser.

This report focuses exclusively on the chemical behaviour and toxicity of uranium. Effects associated with radioactivity and with the decay products of uranium are not discussed or considered in this document. This is consistent with international regulator reviews that have considered the chemical toxicity of uranium to present a substantially greater environmental hazard than its radiotoxicity (ATSDR 2013, CCME 2007).



2.0 GEOLOGY AND GEOCHEMISTRY

2.1 General Geology The mean crustal abundance of U varies with rock type, and ranges from <0.01 mg/kg in ultramafic rocks to 3.3 to 3.7 mg/kg in clays and shales (Parker 1967). Elements with similar crustal abundances include molybdenum and tin (CRC 2005).

Uranium generally occurs as an oxide mineral (i.e., bound to oxygen). The major ore deposits are associated with fracture zones and intersections of faults and unconformities

1, and particularly at

unconformities between Paleoproterozoic or older (>1,600 Ma) basement rocks and middle Proterozoic (1,000-1,600 Ma) sandstone sequences (Christie & Brathwaite 1999). Such deposits, which are principally located in Canada and Australia, account for a third of all known U resources. Mesozoic and Tertiary sandstone deposits account for another third, but are less important as economic resources.

In New Zealand, U mineral deposits are restricted to the West Coast, particularly within an area from the Buller Gorge in the north to the Pororari River in the south (Christie & Brathwaite 1999). West Coast beach sand contains up to about 30 mg/kg U (Roberts & Whitehead 1991).

2.2 Geochemistry Uranium has five oxidation states, 0 (metallic) and III through VI. The IV and VI oxidation states are the most stable and therefore of most environmental significance. The tetravalent U

IV state is dominant in mineral

phases such as uraninite (pitchblende, UO2). In oxidising environments, the uranyl cation UVI

O22+

forms.

The mobility of the uranyl cation is strongly dependent on pH (Echevarria et al. 2001), the presence of complexing anions such as carbonate or citrate (Ebbs et al. 1998, Echevarria et al. 2001, Mihalik et al. 2012, Vandenhove et al. 2007, Zheng et al. 2003), adsorbing phases such as clays and organic content (e.g., Bachmaf et al. 2010, Prikryl et al. 2001, Yamaguchi et al. 2009, Zielinski et al. 2006) or iron and manganese oxides (reviewed in ATSDR 2013). Consequently, in brief,

In reducing conditions, immobile UO2 forms.

In oxidising, acidic conditions, uranyl ion is dominant but readily adsorbs to common binding phases, except in the presence of certain chelating ions, such as citric acid.

In oxidising, neutral conditions, the uranyl ion forms insoluble hydroxides.

In oxidising, alkaline conditions where carbonate concentrations are high relative to phosphate, moderately soluble and mobile UO2(CO3)n species form.

3.0 URANIUM IN PHOSPHORITE

3.1 Phosphorite Elevated U concentrations in phosphorite minerals were recognised at the start of the twentieth century (Strutt 1906). Uranium can be concentrated in phosphorite because the element adsorbs onto phosphatic minerals such as apatite, a principal constituent of phosphorite (Fouad 2010) and/or codeposits in the same conditions (Baturin & Kochenov 2001).

1 A geological term for a break in sediment deposition.



A summary of U concentrations in phosphorite deposits is in Table 1. The variation in U abundances between phosphate rock samples is primarily dependent on their depositional environments.

Table 1: Uranium content of phosphorites by location.

Phosphorites Uranium concentrations

Global average 751

United States 8-9001,2

Mexico and South America 8-2742

Pacific Islands 15-1212,3,4

Minjingu Deposit (Tanzania) 337-3775

Morocco 76-1365

Egypt 59-1195

Jordan 42-1275

Notes: All units mg/kg, values represent reported ranges. 1 Baturin & Kochenov 2001. 3 Menzel (1968) range of reported medians. 2 FSNZ (2014). 3 Taylor (2007). 4 Makweba & Holm (1993). 5 Erdem et al. (1995).

Baturin & Kocherov (2001), in a review of U in phosphorite, presented data that indicated that U enrichment is greater in more recent phosphorite formations than in older deposits (Table 2). The difference in enrichment was attributed to gradual chemical changes in the older deposits as they became more crystalline, and are exposed to oxic seawaters (Baturin & Kochenov 2001).

Table 2: Uranium content of phosphorite deposits by age of deposit (after Baturin & Kochenov 2001).

Source Mean U concentration, mg/kg

Early Cambrian 16

Middle Cambrian 39

Late Cambrian 32

Ordovician 35

Carboniferous 41

Permian 90

Jurassic 40

Cretaceous 105

Paleocene 150

Eocene 110

Miocene 110

Pliocene-Holocene 75



3.2 Uranium in Chatham Rise Phosphorite Although the Chatham Rise phosphorite resource has been known for more than 60 years and has been the subject of ongoing prospecting, it has never been mined.

Phosphorite nodules on the Chatham Rise were discovered during surveying undertaken in the early 1950s (Reed & Hornibrook 1952). Since the discovery of phosphorites on the Rise, a number of studies have investigated the phosphorite nodules, the associated sediments and their geological setting. The most

intensive period of research was conducted between 1975 and 1981. Between 1975 and 1978, the New Zealand Oceanographic Institute (NZOI) carried out four cruises to the Chatham Rise to study the phosphorite deposits (Cullen & Singleton 1977; Cullen 1978, 1980). In 1978, a joint cruise between NZOI and the Bundesanstalt fur Geowissenschaften und Rohstoffe (BGR) used the research vessel (R/V) Valdivia (Kudrass & Cullen 1982). In 1981, NZOI and BGR conducted a further cruise using the R/V Sonne (Von Rad 1984).

Formation of the Chatham Rise phosphorite is ascribed to mid- to late-Miocene polar upwelling over the period 5 to 16 million years ago. The polar upwelling brought phosphate-rich water into the photic zone, increasing its pH and rendering the water supersaturated with respect to apatite. Phosphorite precipitated out at the sediment/water interface and/or in interstitial pore waters. Reworking processes concentrated apatite into indurated phosphorite nodules lying on and within the uppermost sediments of the seabed (Hughes-Allan 2011). The nodules range in size from around 0.5 to 350 mm, with a crudely concentric structure (Cullen 1987). The sediment matrix comprises unconsolidated, glauconitic sandy mud (Cullen 1987: glauconite is a green-hued iron silicate mineral).

Available data for U and P abundances in bulk samples from the Chatham Rise phosphorites are summarised in Table 3.

Table 3: Summary of U and P data in bulk samples from Chatham Rise surveys.

Parameter Mean Median Min Max IQR* N

Uranium (mg/kg) 155 131 27 524 74 117

Phosphorus (wt %) 9.3 9.5 2.6 11.1 0.6 105

P:U (unitless) 720 730 220 1,640 350 105

Notes: P:U values determined using raw data. A U:P value derived from summary statistic values for U and P will not match the

reported values because of skewness in both U and P data. * I QR = Inter-quartile range.

The data were sourced from:

Sixty-six bulk samples from the Valdivia survey (Kudrass & Cullen 1982).

Twenty-six samples from the Sonne survey for which the proportions of fine (1 mm to 8 mm) and coarse (>8 mm) were known (Von Rad & Rösch 1984).

Thirteen samples from the Dorado survey for which the proportions of fine (2 mm to 8 mm) and coarse (>8 mm) were known.

Twelve samples reported in scientific literature (Kolodny & Kaplan 1970, Cullen 1978) uranium only.



Sampling methods for all bulk samples collected in all surveys were similar; no sorting of fragments was undertaken in any survey (Kudrass H, pers comm). Results for individual grain-size fractions were excluded because they are not considered representative of what will be mined from the Rise (i.e., mined samples will contain a mix of fine and coarse material).

Specifically, the samples excluded from the calculation of a mean value were:

Grain-size analyses for a single nodule collected from Station 291 during the Valdivia cruise.

Samples from the Sonne cruise for which data were only reported for the fine fraction (five samples) or only the coarse fraction (20 samples).

Grain-size analyses for a single nodule collected from Station 120GG during the Sonne cruise.

All data are provided in Appendix A.

Uranium data were skewed right, i.e., most values were lower than average, but rare higher results distorted the mean (median < mean). The mean abundance for P was 9.3 wt % (and data were skewed left; median > mean). The mean ratio of P to U was 716 (based on individual calculations). Prior to the Dorado survey, the minimum cut-off for samples was 1 mm, in the Dorado sample, the cut-off was 2 mm. However, as shown in Figure 1, there was little difference between bulk data mean values for the Dorado and Valdivia voyages, along with those data reported in Cullen (1978).

Figure 1: Violin plot of uranium abundances in bulk samples from Chatham Rise surveys. Bulges in the outlines (violins)

indicate greater numbers of samples.



The results of more general size fraction analysis (>1-2 mm - >undertaken on samples from the Sonne and Dorado cruises indicate that uranium abundance is typically greater in coarser material and lower in finer material. These results are presented in Figure 2, along with the distribution of U in bulk samples, and include samples for which no bulk analysis was undertaken (refer above). A summary of these data are provided in Table 4.

Table 4: Summary of U and P data in fine and coarse samples from the Dorado and Sonne cruises.

Parameter Grain Mean Median Min Max IQR* n

Uranium (mg/kg)Fine 158 166 9.0 305 49 44

Coarse 226 222 20 476 178 59

Phosphorus (wt %)Fine 9.2 9.7 1.8 11.0 0.7 44

Coarse 8.5 8.9 2.1 11.7 1.2 59

P:U (unitless)Fine 660 560 300 2,040 164 44

Coarse 595 407 84 4,550 381 59

Notes: P:U values determined using raw data. A U:P value derived from summary statistic values for U and P will not match the

reported values because of skewness in both U and P data. * IQR = Inter-quartile range.

Figure 2: Stacked distributions of uranium in samples collected from the Chatham Rise surveys.



Statistical analysis of the coarse and fine data in Table 4 using the non-parametric Wilcoxon rank sum test confirmed that U abundances are significantly different in coarse fractions than in fine fractions (p<0.05). The cause of this difference between fractions has been attributed to larger phosphorite nodules having a proportionately greater amount of U-rich apatite material, whereas finer grains have higher proportions of low-U glauconitic material (Von Rad & Rösch 1984).

The Valdivia samples generally come from the western part of the deposit, the Sonne samples generally come from the central and eastern part of the deposit, and the Dorado samples from the western and central areas. The increased uranium content with grain size explains the difference between relatively high results for U in samples from the Sonne survey (and those data reported in Kolodny & Kaplan 1970) compared to the Valdivia and Dorado surveys (which had typically lower uranium abundances). The samples from the area surveyed during the Sonne survey were generally coarser than the samples collected during the other surveys.

Figure 3 provides a summary of all data described above.

Figure 3: Histogram of U concentrations in phosphorite nodules from the Chatham Rise.



4.0 URANIUM IN PHOSPHATE FERTILISERS

4.1 Phosphorites used in New Zealand The traditional New Zealand sources of phosphate for fertiliser were phosphorites mined from Nauru and Christmas Island in the Pacific. Fertilisers from Christmas Island contained relatively low U concentrations, but concentrations of U in fertiliser from Nauru had moderate levels (refer Table 2). Phosphorite for New Zealand fertilisers are now typically sourced from the Middle East, northern Africa and China, in which uranium levels are also moderate (FANZ 2014: refer Table 2). Phosphorite from Vietnam and Peru was recently sighted on sale in New Zealand (R Wood, CRP, pers comm.)

4.2 Processing Phosphorites into Fertilisers The amount of U in a given fertiliser depends on both the processing method and the source of the material.

drying and granulating the result. Acid-volatile constituents such as carbonate and fluoride are removed in the process (NZIC 1998, 1999). Because a weight of acid has been added, superphosphate contains less phosphorus and less uranium by weight than phosphorite the P:U ratio does not change. Since fertilisers are applied on a P loading basis, the associated uranium loading does not change whether phosphorite is applied raw or as processed superphosphate.

In most other countries, the superphosphate production process is different. Calcium sulfate is precipitated aking a small proportion of the uranium with it.

The difference arises because, in New Zealand, soils often have suboptimal sulphur levels, and the calcium sulphate has fertiliser value in itself. In other processes, phosphoric acid may be used for acidulation,

ammonium phosphate fertilisers. Potassium may also be added for cropping use.

4.3 Uranium in Current New Zealand Fertilisers CRP could find no public record of the level of uranium in commercial fertilisers. To determine representative values of uranium concentration, samples were purchased from outlets in the North and South Islands. Manufactured products with several concentrations of phosphate and potassium were purchased (Ballance Superten and Superten 10k, Ravensdown Superphosphate and +20 % Potash Super), as well as (unprocessed) reactive phosphate rock.

Samples were collected at a geographic spread of towns to try to capture some of the variability in the fertiliser chemistry that might arise from different source rocks. The assumption was that even if products were distributed nationally then variations in local sales might result in the availability of fertilisers made from different source rocks. Samples were purchased in Hokitika, Timaru, Nelson, Rolleston, Hornby, Alexandra, Cromwell, Petone, Carterton, Masterton, Hastings, Te Awamutu, Tirau, Kerepehi, Huntly, Feilding and Mangatinoka (R. Wood, CRP, pers. comm).

The samples were prepared by Eurofins in Auckland and analysed by Hill Laboratories in Hamilton. Uranium and cadmium levels were analysed by strong acid digestion and inductively coupled plasma mass spectrometry. Summary statistics are presented in Table 5 and laboratory reports form Appendix B.

Table 5: Uranium content of New Zealand phosphate fertiliser sources.

Type Number of samples Uranium, mg/kg Cadmium, mg/kg

Phosphorite 9 66 (20-91) 27 (8.1-37)

Superphosphate 21 33 (24-54) 16 (9.1-23)

Potassic super 7 22 (19-29) 9.5 (7.8-14)

Notes: Values are means with reported ranges in parentheses.



5.0 BACKGROUND CONCENTRATIONS IN NEW ZEALAND SOILS Few data are available for background abundances of U in New Zealand soils. Based on Table 6,background concentrations of U in New Zealand soils are estimated to be typically about 1 mg/kg, with moderate variation from location to location. It is important to recognise that soil uranium concentrations depend on analytical -ray fluorescence, or radiological methods may generate higher results than partial digestions with strong acids such as aqua regia (a mixture of concentrated nitric and hydrochloric acids), because they can detect uranium trapped in silicate materials, which partial digestions cannot. There is no such problem for fertilisers, which are normally completely soluble in strong acid.

In considering the chemistry of uranium in soils, uranium concentrations determined via strong acid extractions are more useful, since silicate-bound uranium is not chemically or biologically active.

Table 6: Uranium background concentrations in New Zealand soils.

Location Soil type Analytical methodMean uranium,mg/kg

Reference

Bay of Plenty Native forest soils Aqua regia/ICPMS 0.52 Guinto (2011)

Whatawhata (Waikato)

Hill country pastoral unfertilised

Aqua regia/ICPMS 1.2 Schipper et al. (2011)

Waikato Aqua regia/ICPMS 0.79WRC 2011,

Taylor et al. (2011)

North Island Dairy land circa 1950sTotal dissolution/

-spectrometryRange 0.6-2.3(n = 4)

Taylor (2007)

Winchmore (Canterbury)

Pastoral unfertilised Aqua regia/ICPMS 1.1 McDowell (2012)

Variousmid-1970s

Inferred from radium concentration

1.9Dobbs & Matthews (1976)

NZ-wide Aqua regia/ICPMS 1.1 McDowell et al. (2013)

6.0 ENVIRONMENTAL GUIDANCE There are no formal New Zealand guidelines for U in soils.

The Canadian Council of Ministers of the Environment (CCME 2007) has derived Soil Quality Guidelines (SQGs) for the ingestion of U to protect human health and the environment. These guidelines are presented in Table 7. These guidelines consider that uranium toxicity arises largely from chemical toxicity, rather than radiological effects, a conclusion backed by other regulators (e.g., ATSDR 2013, WHO 2001).

Table 7: CCME (2007) soil quality guideline values for U in agricultural soils (all data mg/kg).

Guideline Limiting pathway SQG

Human health Soil ingestion, inhalation and dermal exposure (toddler) 23

Environmental healthVascular plants and soil invertebrates 500

Primary consumer mammals (rabbit) 33



Based on a review of toxicological data, Sheppard et al. (2005) proposed thresholds of 250 mg/kg for the protection of terrestrial plants, and 100 mg/kg for protecting other soil biota. The latter value was also considered to be protective of sediment biota, which is of interest should fertiliser and soil particles be washed into fresh water bodies. Sheppard et al. (2005) considered that these guideline values for plants and soil biota should also protect birds, which appear relatively tolerant of uranium.

7.0 ENVIRONMENTAL MOBILITY

7.1 Accumulation of Uranium in Fertilised Soils

7.1.1 International studies

There is a direct link between phosphate fertiliser application and U concentrations in soils. International examples of U accumulation in soils as a result of the use of phosphate fertilisers include cases in Australia (Lottermoser 2009), Brazil (Conc Bonotto 2003), England (Rothbaum et al. 1979), France (Wetterlind et al. 2012), Germany (Birke et al. 2009), Ireland (Tunney et al. 2009), Japan (e.g. Takeda et al. 2006, Yamaguchi et al. 2009), Mexico (Guzmán et al. 2006), Sri Lanka (Chandrajith et al. 2009), Serbia (Stojanovic et al. 2006), the United States (Zielinski et al. 2006), and New Zealand (refer Section 6). The highest resulting concentration of U appears to have been 7.0 mg/kg in a rice paddy soil from Medawachchiya, Sri Lanka (Chandrajith et al. 2009)

2.

7.1.2 New Zealand studies

Golder has identified four studies of uranium accumulation at specific sites in New Zealand:

Rothbaum et al. (1979) found uranium accumulating at approximately 0.026 mg/kg/yr on a pastoral farm at Papatoetoe between 1954 and 1975.

Taylor (2007) found uranium accumulating at 0.015 to 0.047 mg/kg/yr on four North Island dairy farms between circa 1950 and 1992.

McDowell et al. (2012) found uranium accumulating at 0.006 and 0.009 mg/kg/yr at Winchmore sheep/beef research station, Canterbury, between 1958 and 2005, in soils receiving 18 and 36 kg P/ha/yr as superphosphate.

Schipper et al. (2011) found uranium accumulating at 0.019 to 0.067 mg/kg/yr at the Whatawhata hill country research farm near Hamilton between 1983 and 2006, on blocks receiving 30 to 100 kg P/ha/yr,predominantly (from 1989 onward) as imported triple superphosphate.

Mean concentrations of U in Bay of Plenty topsoils were higher in a range of agricultural land uses than in natural soils (including dairying, kiwifruit orchards and maize cropping: Guinto 2011) but had not significantly changed between 1999 and 2009 (Guinto 2012).

Results for U in Waikato soils by land use indicate that land use has an effect on U abundances in soils (Figure 4). Uranium abundances in soils were typically higher for horticultural, cropping and pastoral soils and lower in native or plantation forest, consistent with a significant contribution from fertiliser (Taylor et al. 2011). The 95

th percentile of the U distribution in Waikato horticultural and arable soils was 4.1 mg/kg, while

in pastoral soils it was 3.1 mg/kg (WRC 2011).

2 Guzman et al. report up to 50 mg/kg UO22+, but this is approximately 100-fold more than the amount of uranium reported to have been applied, suggesting a calculation error.



Figure 4: Uranium in Waikato soils (from Taylor et al. 2011) (middle line = median, coloured box = upper and lower quarters, whiskers = 95 % confidence interval, dots = samples outside 95 % confidence interval).

7.2 Mechanisms of Accumulation As U

IV is insoluble and U

VI is effectively bound to clays and organic matter (refer Section 2.2), applied U has

been observed to be retained in the upper few centimetres of the soil profile (Rothbaum et al. 1979, Stojanovic et al. 2006, Yamaguchi et al. 2009, Smidt 2011, McDowell 2012) even in very sandy soils (Zielinski et al. 2006). In experiments where concentrations of U in applied fertiliser were measured, almost all applied U was still present, several decades after fertiliser trials commenced (Rothbaum et al. 1979,Tanaka et al. 2006).

However, in another experiment where soils were subject to border-dyke irrigation (McDowell 2012), a (e.g. McDowell 2010), accumulation was considerably

less than would be expected based on fertilisers of the time. Smidt (2011) summarises German studies of groundwater and tapwater that show a strong geological influence, with uranium concentrations highest in waters of former mining catchments, but also elevated under carbonate-rich, organic-poor, freely draining loess soils used for agriculture. Similarly Wetterlind et al. (2012) report uranium accumulation in two long-term French fertiliser trials, but accumulation was not statistically significant in a third trial, in a high-carbonate soil (27.2 % CaCO3).



In New Zealand agricultural soils, which are typically moderately acid (pH > 5.5), with relatively high organic matter, weathered clay and/or iron content, strong U retention in topsoils is expected. New Zealand has no carbonate-rich agricultural soils (Mackay, AgResearch, pers. comm).

By the same token, since U is retained in surface soil, U loss through (overland) runoff could occur in some circumstances. New Zealand has significant areas of soils that are considered high risk for P loss in overland flow, including sands, podzols, peats, Pallic soils and some Recent soils (Mackay, AgResearch, pers. comm.). Land that was formerly subject to border-dyke irrigation may also have lost U in discharged irrigation water.

7.3 Uranium Uptake

7.3.1 Plants

Plant uptake of uranium from agricultural soils containing low to moderate uranium concentrations appears to be low (ATSDR 2013, CCME 2007, WHO 2001). Plant uptake appears to increase in highly contaminated soils.

Soil-to-vegetable bioconcentration factors (BCFs) can be estimated from uranium in food datasets. UKFSA (2004) and Anke et al. (2009) report U concentrations in foods of the United Kingdom and of Germany, respectively. Assuming that these foods are generally grown in soils with typical background U concentrations, around 2 mg/kg, the diet-weighted mean BCF for U is approximately 0.01 for each of root, tuber and leafy vegetables (Appendix C: based on New Zealand Total Diet Survey daily intake for 1 to 3year-old: NZFSA 2011). The assumption of background concentrations is likely to be conservative since U-containing phosphate fertilisers have long been used in these countries (Rothbaum et al. 1979, Schnug 2012).

There are no known terrestrial plants that are hyperaccumulators of uranium (Ebbs et al. 1998). Waterplants growing in former U mining areas have been reported to contain up to 0.5 % U by dry weight (Favas et al 2014). In the studies of Anke et al. (2009) and Kuwahara (1997), some mushrooms had higher concentrations of U than any sampled vegetable, though seaweeds had the highest concentrations among foodstuffs sampled.

Predicting uranium uptake in fertilised soils is difficult. Plant species can vary substantially in their U uptake capacities, and those capacities vary from soil to soil (Mortvedt 1994). Each different combination of plant and soil may have a unique curvilinear U uptake relationship (Shtangeeva 2010). Changes in soil pH and redox potential, or the addition of U

VI-complexing ions, may have a substantial effect on U mobility (refer

Section 2) and hence on plant uptake (Fresquez et al. 1998, Hegazy & Emam 2001, Hossner et al. 1998, refer also review in ATSDR 2013). There is good evidence that uranium uptake varies significantly on a diurnal timescale (Shtangeeva 2010).

Moreover, many studies of uranium uptake by plants have been undertaken in highly contaminated areas or in spiked nutrient solutions. In these circumstances, U is likely to be much more bioavailable (Shtangeeva 2010). Among BCFs tabulated in the review of CCME (2007), BCFs are significantly higher in studies of Port Hope soils, contaminated to approximately 30 mg/kg U by a nearby uranium smelter (Tracy et al. 1983, cited in CCME 2007); in soils spiked to 100 to 600 mg/kg U with highly soluble uranyl nitrate (Sheppard et al. 1989, Shahandeh and Hossner 2002, cited in CCME 2007); and in soils containing 100-600 mg/kg U due to accumulation of natural uranium in carbonate-rich groundwater (van Netten and Morley 1983).

Nonetheless, some consistent themes emerge from the literature. Uranium BCFs for vegetables are typically substantially less than 1; that is, U uptake is low in most circumstances. U accumulates mainly in or on the roots of plants (ATSDR 2013, etc.). This is considered to be due to physical and biochemical barriers; in addition, plants appear to be protected from U by mycorrhiza, root fungi that stabilise U and prevent it from entering plant tissue (Chen et al. 2005). Root-to-shoot translocation of U is often limited (Singh et al. 2005), and distribution of U in plants is similar to trends for other environmentally significant elements with roots > leaves > straw > seeds (Puschenreiter et al. 2005).



7.3.2 Animals

Animal uptake of uranium from agricultural soils containing low to moderate uranium concentrations appears to be low. There is no evidence of bioaccumulation in the food chain. When animals do take up U, it partitions principally to kidney and to a lesser extent liver and bone (ATSDR, CCME 2207, WHO 2001).

Smith & Black (1975) reported concentrations of 6.8 µg/kg U in the livers (and lower concentrations in muscle tissue) of cattle grazing an area near an enriched U processing plant in Colorado. Rayno (1983) considered the transfer of U from soils to plants to cattle through to humans. In that study, it was estimated that only a very small proportion of the U taken up by plants would be transferred to humans, equivalent to less than 1 µg/day per L (or kg) consumed.

7.4 Predicted Changes Associated with Phosphorite Application Based on the previous sections, uranium is predicted to be effectively immobile in agricultural soils receiving phosphate fertiliser. Exceptions could include strongly acid soils (pH < 5); alkaline, carbonate-rich soils; and very sandy or stony soils with little clay, organic matter or iron content. These environmental conditions are not typical of New Zealand agricultural soils. Plants and animals are not expected to remove U to any significant extent. Consequently, U is expected to accumulate in soils.

The rate of uranium accumulation, expressed as a loading in kg/ha, would therefore depend principally on the P fertiliser application rate, the mean U concentration in applied fertiliser. The P fertiliser application rate is primarily a function of farm type, with higher rates expected in more intensive land uses such as horticulture or dairying (PCE 2012). The mean U concentration is primarily a function of the source of the raw material; in New Zealand practice, U loadings would be the same whether or not the phosphorite was processed into superphosphate (Section 4). Topsoil U concentrations would depend on the rate of

soil biota, plants and stock.

Chatham Rise phosphorite contains a mean uranium concentration of 155 mg/kg (Section 3), approximately 2.5 times greater than the mean of the commercially available phosphorites recently sampled by CRP (Section 4) and approximately 1 to 2 times greater than the reported range for Moroccan phosphorite, the principal source of New Zeala since the mid-1990s (Section 2). Accordingly, the rate of U accumulation would increase, potentially double, if Chatham Rise phosphorite became the principal raw material in future.

Currently, uranium concentrations in Waikato agricultural soils are rarely greater than 4 mg/kg (Section 7). Given a natural background on the order of 1 mg/kg (Section 5), this indicates U accumulation of less than 3 mg/kg after some decades of P fertiliser application. Even should the rate of accumulation double, many more decades would pass before intensively farmed soils exceeded the Canadian soil guideline value of 23 mg/kg for uranium in agricultural soils.

8.0 SUMMARY The phosphorite resource on the Chatham Rise has a higher mean uranium concentration than other phosphorites used as raw materials for New Zealand fertilisers. Uranium is expected to be effectively immobile in agricultural soils, and will therefore accumulate as fertiliser application continues. Extensive use of Chatham Rise phosphorite as a raw material would increase the rate of uranium accumulation. However, many more decades would pass before intensively farmed soils exceeded identified international soil guideline values for uranium.



9.0 LIMITATIONS Your attention is draw D. The statements presented in that document are intended to advise you of what your realistic expectations of this report should be, and to present you with recommendations on how to minimise the risks to which this report relates which are associated with this project. The document is not intended to exclude or otherwise limit the obligations necessarily imposed by law on Golder Associates (NZ) Limited, but rather to ensure that all parties who may rely on this report are aware of the responsibilities each assumes in so doing.

10.0 REFERENCES ATDSR 2013. Toxicological profile for uranium. Agency for Toxic Substances and Disease Registry. February 2013.

Baturin GN, Kochenov AV 2001. Uranium in Phosphorites. Lithology and Mineral Resources 36: 303-321.

Birke M, Rauch U, Lorenz H 2009. Uranium in stream and mineral water of the Federal Republic of Germany. Environ Geochem Health 31: 693-706.

CCME 2007. Canadian soil quality guidelines for uranium: Environmental and human health. Canadian Council of Ministers of the Environment Scientific Supporting Document.

Chandrajith R, Seneviratna S, Wickramaarachchi K, Attanayake T, Aturaliya TNC, Dissanayake CB 2009. Natural radionuclides and trace elements in rice field soils in relation to fertilizer application: study of a chronic kidney disease area in Sri Lanka. Environmental Earth Sciences 60: 193-201.

Chen B, Roos P, Borggaard OK, Zhu YG, Jakobsen I 2005. Mycorrhiza and root hairs in barley enhance acquisition of phosphorus and uranium from phosphate rock but mycorrhiza decreases root to shoot uranium transfer. New Phytol 165: 591-8.

Christie T, Braithwaite B 1999. Mineral Commodity Report 19 Beryllium, gallium, lithium, magnesium, uranium and zirconium. New Zealand Mining 26: 27-42.

Co 2003. Use of U-isotope disequilibrium to evaluate the weathering rate and fertilizer- -418.

CRC 2005. Handbook of chemistry and physics. 85th edition. CRC Press, Boca Raton, Florida.

Cullen DJ 1978. The uranium content of submarine phosphorite and glauconite deposits on Chatham Rise, east of New Zealand. Marine Geology 28: 67-76.

Dobbs J, Matthews K 1976. A survey of naturally occurring radionuclide concentrations in New Zealand soils. New Zealand Journal of Sciences, 243-247.

Ebbs SD, Brady DJ, Kochian LV 1998. Role of uranium speciation in the uptake and translocation of uranium by plants. Journal of Experimental Botany 49: 1183-1190.

Erdem E, Tinkiliç N, Yilmaz VT, Uyanik A, Ölmez H 1995. Distribution of uranium in the production of triple superphosphate (TSP) fertilizer and phosphoric acid. Fertilizer research 44: 129-131.

FANZ 2014. Uranium in soil, plants and fertiliser. Fertiliser Association of New Zealand Technical Paper. July 2014.



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August 2014Report No.

APPENDIX A Uranium in Chatham Rise Phosphorites: Raw Data

APPENDIX AUranium and Phosphorus Data for Chatham Rise Phosphorites

August 2014Reference No. 1178207517 1/6

Cruise Site Type Fraction U (mg/kg) P2O5 (%) P (%) P:U

Sonne 1A >8 Coarse 295 20.6 8.97 304

Sonne 1B >8 Coarse 349 7.3 3.19 91.3

Sonne 1C >8 Coarse 255 22.7 9.9 388

Sonne 24 >8 Coarse 316 26.4 11.5 365

Sonne 24 >1-<8 Fine 118 24.3 10.6 897

Sonne 25 >8 Coarse 242 22.1 9.64 398

Sonne 62 >8 Coarse 176 23 10 569

Sonne 66 >8 Coarse 309 21.9 9.56 309

Sonne 94 >8 Coarse 240 26.7 11.7 485

Sonne 98 >8 Coarse 47 20.5 8.95 1900

Sonne 110 >8 Coarse 101 19.2 8.37 829

Sonne 110 >1-<8 Fine 119 24.8 10.8 911

Sonne 111 >8 Coarse 113 23 10 887

Sonne 111 >1-<8 Fine 132 24.6 10.7 813

Sonne 167 >8 Coarse 468 19.2 8.39 179

Sonne 167 >1-<8 Fine 172 23 10 583

Sonne 183 >8 Coarse 211 21.4 9.35 443

Sonne 246 >8 Coarse 165 21.2 9.23 559

Sonne 246 >1-<8 Fine 185 22.5 9.82 531

Sonne 314 Bulk Bulk 216 21.1 9.21 426

Sonne 321 >8 Coarse 299 18.5 8.07 270

Sonne 321 >1-<8 Fine 193 22.4 9.77 506

Sonne 324 >1-<8 Fine 182 22.5 9.84 540

Sonne 330 >1-<8 Fine 159 22.6 9.88 621

Sonne 333 >1-<8 Fine 164 21.6 9.42 574

Sonne 334 >8 Coarse 169 21.1 9.2 544

Sonne 334 >1-<8 Fine 177 21.1 9.23 521

Sonne 340 >8 Coarse 222 19.2 8.36 377

Sonne 340 >1-<8 Fine 199 21 9.18 461

Sonne 341 >8 Coarse 314 19.8 8.66 276

Sonne 341 >1-<8 Fine 190 22.4 9.76 514

Sonne 346 >8 Coarse 173 23.4 10.2 590

Sonne 346 >1-<8 Fine 151 22.1 9.64 639

Sonne 350 >8 Coarse 335 22 9.6 287

Sonne 354 >8 Coarse 92 21.3 9.29 1010

Sonne 354 >1-<8 Fine 162 22.4 9.79 604

Sonne 375 >8 Coarse 420 16.9 7.37 175

Sonne 380 >8 Coarse 338 17 7.44 220




Sonne 380 >1-<8 Fine 172 21 9.18 534

Sonne 381 >8 Coarse 94 17.5 7.63 812

Sonne 381 >1-<8 Fine 167 21.6 9.42 564

Sonne 385 >8 Coarse 125 19.7 8.61 689

Sonne 390 >8 Coarse 385 21.1 9.2 239

Sonne 390 >1-<8 Fine 136 16.7 7.27 535

Sonne 399 >8 Coarse 308 18.8 8.18 266

Sonne 399 >1-<8 Fine 177 19.2 8.38 474

Sonne 409 >8 Coarse 287 24 10.5 364

Sonne 409 >1-<8 Fine 194 20.6 9 464

Sonne 412 >8 Coarse 133 19.7 8.59 646

Sonne 412 >1-<8 Fine 121 16.6 7.22 597

Sonne 414 >8 Coarse 190 17.7 7.74 407

Sonne 414 >1-<8 Fine 131 14.8 6.44 491

Sonne 417 >8 Coarse 134 11.7 5.09 380

Sonne 422 >8 Coarse 262 17.8 7.79 297

Sonne 434-A >8 Coarse 254 4.88 2.13 83.8

Sonne 434-Z >8 Coarse 476 15.4 6.74 142

Sonne 444-A >1-<8 Fine 305 20.9 9.11 299

Sonne 444-B >1-<8 Fine 187 22.4 9.75 522

Sonne 468 >8 Coarse 220 24.2 10.5 479

Sonne 483 >8 Coarse 230 22.4 9.78 425

Sonne 483 >1-<8 Fine 167 22.7 9.89 592

Sonne 484 >8 Coarse 407 19.9 8.68 213

Sonne 486 >8 Coarse 127 19.7 8.59 676

Sonne 486 >1-<8 Fine 174 22.4 9.77 562

Sonne 488 >8 Coarse 214 20.1 8.78 410

Sonne 488 >8 Coarse 459 16.2 7.06 154

Sonne 488 >1-<8 Fine 173 22.3 9.74 563

Sonne 502 >8 Coarse 168 18.4 8.05 479

Sonne 502 >1-<8 Fine 175 23.2 10.1 578

Sonne 519 >8 Coarse 276 20.8 9.08 329

Sonne 519 >1-<8 Fine 179 22.6 9.88 552

Sonne 525 >8 Coarse 270 19.4 8.48 314

Sonne 525 >1-<8 Fine 202 21.5 9.38 464

Sonne 526 >8 Coarse 445 21 9.14 205

Sonne 526 >1-<8 Fine 159 23 10 632

Sonne 541 >8 Coarse 110 18.9 8.26 751




Sonne 545 >8 Coarse 20 20.9 9.11 4550

Sonne 545 >1-<8 Fine 249 25.3 11 443

Cullen H640 Bulk Bulk 201 NA NA NA



Cullen H667 Bulk Bulk 95.1 NA NA NA


Kolodny KP8 Bulk Bulk 117 NA NA NA







Dorado DD04 >2-<8 Fine 84 22.7 9.91 1180

Dorado DD04 >8 Coarse 119 21 9.14 768

Dorado DD06 >2-<8 Fine 83 22.6 9.88 1190

Dorado DD06 >8 Coarse 72 21 9.17 1270

Dorado DD14 >2-<8 Fine 123 22.2 9.69 788

Dorado DD14 >8 Coarse 33 20.9 9.13 2770

Dorado DD18 >2-<8 Fine 82 22.1 9.66 1180

Dorado DD18 >8 Coarse 86 21.4 9.33 1080

Dorado DD25 >2-<8 Fine 163 19.5 8.49 521

Dorado DD25 >8 Coarse 283 18.9 8.23 291

Dorado DD27 >2-<8 Fine 171 18.7 8.16 477

Dorado DD27 >8 Coarse 309 17.2 7.51 243

Dorado DD28 >2-<8 Fine 9 4.2 1.83 2040

Dorado DD28 >8 Coarse 67 9.96 4.35 649

Dorado DD32 >2-<8 Fine 183 14.8 6.48 354

Dorado DD32 >8 Coarse 239 13.1 5.7 238

Dorado DD40 >2-<8 Fine 163 19.9 8.69 533

Dorado DD40 >8 Coarse 243 18.7 8.16 336

Dorado DD42 >2-<8 Fine 109 22.5 9.84 902

Dorado DD42 >8 Coarse 108 21.5 9.39 869

Dorado DD45 >2-<8 Fine 118 23 10 850

Dorado DD45 >8 Coarse 121 22.6 9.85 814

Dorado DD46 >2-<8 Fine 149 22.3 9.73 653

Dorado DD46 >8 Coarse 196 21.3 9.3 475




Dorado DD47 >2-<8 Fine 130 23.1 10.1 774

Dorado DD47 >8 Coarse 198 22.9 10 505

Valdivia 298 Bulk Bulk 145 22 9.59 661

Valdivia 73 Bulk Bulk 100 22.6 9.87 987






























Valdivia 287i Bulk Bulk 151 21 9.16 607













Valdivia 501i Bulk Bulk 141 22.4 9.79 694

























Sonne 24 Bulk Bulk 233 25.5 11.1 478

Sonne 111 Bulk Bulk 118 23.4 10.2 864

Sonne 167 Bulk Bulk 286 21.5 9.4 329

Sonne 246 Bulk Bulk 170 21.5 9.37 552

Sonne 321 Bulk Bulk 271 19.5 8.52 315

Sonne 334 Bulk Bulk 174 21.1 9.22 530

Sonne 340 Bulk Bulk 216 19.6 8.57 396

Sonne 341 Bulk Bulk 280 20.5 8.96 320




Sonne 346 Bulk Bulk 171 23.3 10.2 594

Sonne 354 Bulk Bulk 108 21.6 9.41 873

Sonne 380 Bulk Bulk 334 17.1 7.48 224

Sonne 381 Bulk Bulk 95.7 17.6 7.67 802

Sonne 390 Bulk Bulk 355 20.6 8.97 252

Sonne 399 Bulk Bulk 297 18.8 8.2 276

Sonne 409 Bulk Bulk 271 23.4 10.2 377

Sonne 412 Bulk Bulk 131 19 8.31 636

Sonne 414 Bulk Bulk 181 17.3 7.55 417

Sonne 483 Bulk Bulk 216 22.5 9.81 454

Sonne 486 Bulk Bulk 137 20.2 8.83 646

Sonne 488 Bulk Bulk 201 20.8 9.08 452

Sonne 502 Bulk Bulk 170 19.8 8.65 509

Sonne 519 Bulk Bulk 247 21.3 9.31 376

Sonne 525 Bulk Bulk 260 19.7 8.62 332

Sonne 526 Bulk Bulk 231 22.5 9.81 424

Sonne 545 Bulk Bulk 92.3 22.3 9.72 1050

Dorado DD04 Bulk Bulk 104 21.7 9.46 906

Dorado DD06 Bulk Bulk 75.9 21.6 9.42 1240








Dorado DD42 Bulk Bulk 108 22 9.59 885



Dorado DD47 Bulk Bulk 172 23 10 584



APPENDIX B Chemical Analyses of Current Phosphate Fertilisers

† Indicates tests which are not IANZ Registered.

§Indicates Subcontracted Tests

Signed

All results reported on material AS RECEIVED unless stated otherwise.

Eurofins NZ Laboratory Services Limited, 35 O’Rorke Road, P O Box 12545, Penrose, AUCKLANDWhile all care is taken with analyses, we will not accept any responsibility for their resulting use. These results have been obtained from the sample ‘as

received’ at the laboratory and may not be representative of the bulk material. This report may not be reproduced except in full. FREEPHONE: 0800 695 227 Tel: 09 579 2669 Fax: 09 571 2285 Email: [email protected] Website: www.eurofins.co.nz

O/N:62713 Form No: 5013400

Sampled: 28-Jul-2014

Received: 29-Jul-2014

Reported: 06-Aug-2014

Page 1 of 2

Any interpretation or recommendations are prepared independently by your consultant

Client Details Consultant Details

CRL Energy Ltd Eurofins NZ Laboratories Ltd

PO Box 31-244

LOWER HUTT 5010 Ruakura Research Centre

PO Box 281

10 Bisley Road

Telephone: 04 570 3700 HAMILTON

Property Name Attn: Ben Rumsey

Test Results

Cd† U†

Sample Name Cadmium Uranium

ppm ppm

SY-3 0.2 600

Te Awamutu 16.9 36

Tirau 19.9 37

Kerepehi 18.7 34

Huntly 11.5 28

Ballance Superten 19.9 32

Ravensdown Superphosphate

12.9 28

Ravensdown + 20% Potassic Super

11.0 24

Ravensdown RPR 36.2 69

FB 14.8 33

FR 16.8 31

MR 22.7 54

PB 18.0 33

Mitre10 Petone Tui Superphosphate

19.6 37

Mitre10 Petone Tui SOP 0.5 1

Ravensdown Carterton Superphosphate

18.7 34

Ravensdown Carterton 20% Potassic Super

16.1 28

Ravensdown Carterton RPR

32.7 64

1. Microwave nitric acid digestion is not intended to accomplish total decomposition of the sample, therefore may result in an under-estimation of true totals in some high silicate fertiliser materials.

O/N:62713 Form No: 5013400




Page 2 of 2




PO Box 31-244


PO Box 281

10 Bisley Road



Test Units and Test Methods Test Unit Unit Description Test Method

Cd ppm mg Cd per kg EPA 3051, subcontracted ICP_MS determination

U ppm mg U per kg EPA 3051, subcontracted ICP_MS determination



Signed




Form No: 5013401




Page 1 of 1




PO Box 31-244


PO Box 281

10 Bisley Road



Test Results

Cd† U†


ppm ppm

106/400 Sechura PR 17.1 69

106/401 Jordan PR 6.9 48

106/402 Arao PR 15.3 155

106/403 Christmas Is. PR 26.0 41

106/404 Kouribga PR 10.5 124

106/405 Nth. Carolina PR 46.3 68

106/406 Nauru PR 80.5 68



Cd ppm mg Cd per kg EPA 3051, subcontracted ICP_MS determination U ppm mg U per kg EPA 3051, subcontracted ICP_MS determination



Signed




O/N:6271313042251 Form No: 5013402




Page 1 of 2




PO Box 31-244


PO Box 281

10 Bisley Road



Test Results

Cd† U†


ppm ppm

Ballance Rolleston Super10

15.6 34

Ballance Rolleston Potassic Super

13.6 29

Ballance Rolleston RPR 22.9 91

Ravensdown Superphosphate

12.7 30

Ravensdown Potassic Super

8.1 19

Ravensdown RPR 34.2 70

Ballance Masterton Super10

13.8 32

Ballance Masterton Potassic Super

8.7 19

Ballance Masterton RPR 27.5 89

Ballance Hastings Super10

12.1 32

Ballance Hastings Potassic Super

9.4 26

Ballance Hastings RPR 28.9 86

Farmlands Hastings Super10

12.9 29

Mitre10 Hastingd Yates Superphosphate

19.9 35

Mitre10 Hastings Yates SOP

0.2 1

Mitre10 Hastings Tui Superphospahe

18.6 45

Mitre10 Hastings Tui SOP 0.4 1

Ballance Richmond Super10

9.1 24

Ballance Richmond Potassic Super

7.8 20

Ballance Richmond RPR 8.1 20

Ravensdown Richmond Super P

11.3 26

Ravensdown Richmond Potassic Super

8.1 19

Ravensdown Richmond RPR

36.6 69

O/N:6271313042251 Form No: 5013402




Page 2 of 2




PO Box 31-244


PO Box 281

10 Bisley Road



Test Results

Cd† U†


ppm ppm

Ravensdown Hokitika Super P

12.7 28

Ravensdown Hokitika Potassic Super

10.8 24

Ravensdown Hokitika RPR

32.0 66



Cd ppm mg Cd per kg EPA 3051, subcontracted ICP_MS determination U ppm mg U per kg EPA 3051, subcontracted ICP_MS determination



APPENDIX C Estimates of Uranium Dietary Intake and BCFs



APPENDIX D Report Limitations

APPENDIX DReport Limitations

August 2014Project No. 1178207517 1/1

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