The Geochemical Atlas of Cyprus and the Geological Survey Department Dr Andreas Zissimos

• Why the necessity?

• Project Objectives / Structure • Tender information • Technical Considerations • GSD contribution • Results / Outcome Talk outline

In context…

The primary purpose of geochemistry is to determine quantitatively the chemical composition of the Earth and its parts, and to discover the laws that control the distribution of the individual elements (Victor Goldschmidt 1937; 1954). Applied geochemistry is the application of this knowledge to societal benefit. Geochemical maps are schematic abstractions that greatly facilitate

visualizing

,

understanding

, and

classifying

complex spatial patterns, related to many underlying controlling factors.

Why do we need to map chemical

• Exploration Tool Discovering mineral resources

constituents in soil?

• Environmental purposes Protecting the surface environment that sustains life Improving the efficiency of agriculture and animal husbandry and protects one of the most important resources, underground water.

• Health and medical purposes Studying the behaviour of elements in the food-chain and their health effects on humans and other biota.

All of these, to varying extents, depend upon knowledge of the spatial distribution of the elements in and on the Earth.

Mineral exploration

• Cyprus and its history are directly linked to mineral exploration and exploitation.

• Today mineral exploration, although diminished, is still of high interest especially in view of the prices of mineral commodities such as gold and copper.

• A figure that captures this interest is the number of prospecting permits issued by the Cyprus Mines Service with about

30 prospecting permits in force

and many applications under examination (2010 figures).

• Therefore datasets such as the Geochemical Atlas which would boost this interest are of high importance to Cyprus.

Environmental regulations

• In terms of soil protection Cyprus has not established and enforced a set of statutory limits for toxic elements yet.

• Some references on acceptable limits of toxic elements are applied through the Laws of 2002 on the monitoring of water pollution. These refer mainly to the capacity of soil accepting soil improvers.

• The development of statutory limits for toxic elements in soil based on both natural background knowledge as well as on human health assessment studies.

• Especially in view of the development of the EU directives such us the Soil Framework Directive and the Environmental Liability Directive.

Element

Statutory limits of toxic elements in soil (mg/Kg)

United Kingdom The Netherlands Germany Global soil mean Cyprus

Residential Industrial Optimum Action Playgro und Resid ential Parks and recreational Industrial ?

As Cd Co Cr (tot) Cu Hg Ni Pb Zn

20 8 130 130 8 50 450 500 1400 5000 480 5000 750 29 0.8

20 100 36 0.3

35 85 140 55 12 240 380 190 10 210 530 720 25 10 200 10 200 50 20 400 20 400 125 50 1000 50 1000 140 60 1000 80 2000 5 0.3

10 80 25 0.05

20 17 70 National Inventory of potential sources of soil contamination in Cyprus, 2006 ?

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?

?

?

?

?

?

Land regeneration projects in Cyprus

• Total cost of land regeneration • Impact on local communities • Job generation

Chemical pollution and land regeneration costs

Project

Limni Mine

Public / Private Sector

Private Asbestos mine at Amiandos Public Chemical industries at Mari Public Through a public Tender Kokkinopez oula sulphite mine Oil Refineries Larnaca Total Cost Public

Pollution / Hazard

Mining wastes/ Chemical Mining wastes / carcinogeni c fibres / chemical Chemical / radioactive Mining wastes / chemical Chemical/ hydrocarbo ns

Regeneration Work Time

2010

Land use before / after Cost million Euros 30

Transfer of material (10 million cubic meters of tailings) back to the Mine, landscaping, site regeneration and soil cover, planting Landscaping, road maintenance, ground layering, soil preparation, reforesting and maintenance of plants, maintenance of existing buildings, communal works 2009-2011 1995-2010 Deconstruction of industrial site, cleaning of site and export of chemical and radioactive waste Technical economic study of the site 2006-2007 2010

Industrial / Residential resorts Industrial / Recreational Park Industrial / Industrial Industrial / Recreational Park Industrial / Residential 9 3

>1 ?

41

Geochemical Atlas of Cyprus Project Objectives

• To build a multipurpose database of geochemical data for the soils of Cyprus • Define the geochemical background • Help to establish a set of statutory limits for toxic elements in soils • Use it as an environmental and prospecting tool

Geochemical Atlas of Cyprus The Tender

• Public Tender GSD 2005/12 • Won by the University of New South Wales and their representatives in Cyprus, ADCS International Ltd • Cost of the Tender 680.000 Euros plus VAT • Project duration five years (Initiated in April 2006 and completed in July 2011) • Sampling/analyses/site visits/training • Production of a huge amount of data in GIS format • Publication of the Geochemical Atlas of Cyprus

Project Structure

Geological Survey Department of Cyprus (Client)

GSD Project Committee GSD Director

UNSW Global Ltd (Principal contractor) John Arneil

UNSW-G Project Manager

GSD Analytical section

School of Biological, Earth and Environmental Sciences David Cohen

Principal UNSW Advisor – Geochemistry

Rutherford Mineral Resource Consultants Neil Rutherford

Principal UNSW Advisor – Geochemistry

Andreas Demetriades Consulting Services Andreas Demetriades

Project Coordinator - Cyprus

Actlabs Ltd Iain Dalrymple

Laboratory Manager

Professional and Technical staff Simon Gatehouse

Advisor – Exploration geochemistry

Field technicians

(sampling)

Shawn Laffan

Advisor – GIS

Dorothy Yu

Advisor – Analysis

Geoffrey Taylor

Consultant – GIS and remote sensing

Alistair Dunlop

Consultant – Economic geology

Morteza Jami

Consultant – Laboratory analysis

John Triantafilis

Consultant – Soil geochemistry

Scott Mooney

Consultant – Soil dating

Lab technicians

(

analysis)

Lab technicians

(processing)

Project Workplan

Proposed Actual Final Project Design Specifications Apr ‘06 0 6 Field Sampling Sample Processing Geochemical Analysis Mineralogical Analysis Database Development Data Analysis & modelling Progress & Final Technical Reports Geochemical Atlas of Cyprus Training of GSD staff Ongoing Research collaboration 12 18 24 Month 30 36 42 48 54 60 Official launch

Define the geochemical background?

A crucial term whenever natural or geogenic influences are to be separated from non-natural or anthropogenic influences.

From a geochemical point of view, the term background is equivalent to the absence of an anomaly and the term was first used by exploration geochemists in order to differentiate between the element concentration within unmineralised or unaltered rock matrix and those rock parts that show relative enrichments or depletions.

The term became an important reference with increasing environmental awareness and with a rising number of pollutant investigations in soils and sediments. The term background indicates the content depending on natural factors like lithology, genesis and climate. The term in environmental management is more broadly used to span the full limit of natural variation.

Is "natural" always good?

• Just because a metal concentration is naturally generated does not mean it is not an environmental or health risk.

• Just because metal concentration has been artificially increased by human activity does not mean it poses a risk.

• The problem is to set objective soil statutory limits that reflect values above which there is an undesirable effect on flora and fauna (of which we typically have greatest concern for Homo Sapiens).

How do we set our statutory limits of soil pollution?

• First define "background" – which has scientific, philosophical, socioeconomic aspects • Geochemical Atlas of Cyprus will help the definition • Appreciate the concentrations of elements/ chemicals above which there is significant probability of adverse effects to human health • Set statutory limits well above background and at safe levels for human health

In an environmental investigation of chemical pollution

• One needs to consider background in order to successfully define the extent of pollution • Accordingly define extent of remediation

Cu copper Aqua regia ICP-MS 5,377 sites Keryneia Lefkosia Polis Top soil

(0 – 25 cm)

Ammochostos Larnaca Ayia Napa Pafos Cu Mines Cu (mg/kg)

10,000

Top soil Lemesos Sub soil

(50 – 75 cm)

Cu (mg/kg) Dutch Intervent 800 220 135 115 100 75 65 55 45 35 15

99.9

99 95 90 75 50 25 10 5 1 0.1

10 100 1000 Cu mg/kg

Ba barium Aqua regia ICP-MS 5,377 sites Top soil

(0 – 25 cm)

Lefkara Fmn Dutch Intervention Dutch Target Ba (mg/kg) 800 600 400 330 240 170 120 90 60 40 25

Technical Considerations of the Atlas Project

Key components of the project were defined in the Technical Proposal submitted by UNSW. Implementation issues were discussed and accordingly revised along the way by the GSD and UNSW.

• Sampling grid (introduction of stream sediments, some vegetation, introduction of detailed studies, extra analyses and elements) • Sample processing (decisions on materials and techniques used for sieving filtering and methods of digestion) • Development of QA QC protocols (CRMs QC materials) • Geochemical analyses (instrumentation)

Sampling Options

water sediment humus soil vegetation

Archiving of samples an important issue

If a Geochemical Map is a snap shot of elemental distribution at that moment of time…its important to keep the negatives!!! Soil sample archive for the Geochemical Atlas of Cyprus at the Athalassa storage space of the Geological Survey Department of Cyprus. An important bank for information extraction in the future especially for parameters that change over time.

Two parallel surveys

• Soils: nominal 1 x 1 km grid with a top soil (0 – 25cm) and sub soil (50 – 75cm). • Stream sediment survey: sites on the sampled drainage basins. A total of 89 drainage basins were sampled with a top (0 – 25cm) and bottom (50 – 75cm) sample.

Analytical Techniques

Ion Chromatography (IC) X-ray Fluorescence spectroscopy (XRF) Automatic analysers Carbon Sulfur (CS)

Periodic table of elements analytical techniques

ICP MS XRF IC INAA CNS Automatic analyser

GSD contribution to analytical measurements

• Electrical Conductivity EC • Soluble ionic substituents F , Cl , NO 3 , SO 4 -2 • XRF Silica and other major elements (Al, Fe, Mg, Mn, P) • Total Carbon (TC), Soil Organic Carbon (SOC), Total Sulphur (TS)

TC and SOC distribution in soils of Cyprus

• Carbon is a vital component of soil and its sequestration and cycle are well documented • Its importance has been linked with climate change and the reduction of atmospheric CO2 by using terrestrial ecosystems as carbon sinks • Carbon is contained in minerals and is tightly bound to the fabric of soil and its referred to as Inorganic Carbon (IC) because of its origins being geogenic. Carbon is also contained in soil as soil biota, micro-organisms and debris of plants and this form of carbon is often referred to as Soil Organic Carbon (SOC) • SOC can also be converted to Soil Organic Matter (SOM) a more generic term used for all organic components in soil.

Main pools and flows of the natural global C cycle (in Pg)

ClimSoil report on the review of existing information on the interrelations between soil and climate change, 2008

Human perturbation to the flows of C (in Pg) between the pools

ClimSoil report on the review of existing information on the interrelations between soil and climate change, 2008

TC measurement Collected sample sieved in the field < 2 mm Sample dried @ 100 0 C to remove water content

Experimental

Direct measurement of TC on Automatic analyser Eltra CS800 SOC measurement Heat 2 g sub sample @ 500 0 C for 4 hours and remove SOC and other organic debris Direct measurement of IC on Automatic analyser Eltra CS800 Obtain SOC by calculation SOC = TC - IC

Statistics for all TC and SOC measurements Samples Min Max Mean Median

TC %

3645 0.014

19.255

5.154

4.218

SOC %

2521 0.002

15.463

1.318

1.076

TC Vs Geology

25.000

20.000

15.000

10.000

5.000

0.000

U ltr am afi c Ma fic In tru Vo siv e lca nic s Ma fic C la sti c Si lic ic C la sti c Field Observation C arb on ate s A llu viu m C oll uv iu m

25th Percentile Minimum Mean 50th Percentile Maximum 75th Percentile

Statistics for all TC and SOC measurements Samples Min Max Mean Median

TC %

3645 0.014

19.255

5.154

4.218

SOC %

2521 0.002

15.463

1.318

1.076

SOC Vs Land use

18,000 16,000 14,000 12,000 10,000 8,000 6,000 4,000 2,000 0,000

Agricultural areas Artificial surfaces Forests / Sem i natural areas Land Use Wetlands

25th Percentile Minimum Mean 50th Percentile 75th Percentile 75th Percentile

Carbon estimates based on results

• Soils in Cyprus are considered to be the greatest carbon pool on the island with estimated sequestration of ~4Mt of C in forest soils (Criteria and Indicators For the Sustainable Forest Management in Cyprus Dept Forests 2006), However, this is likely to be an underestimate.

• New estimates of C

Mass of component (Mt) SOC SOC TC All Cyprus Forested areas All Cyprus 23 6 94

Achievements

• The Geochemical Atlas the book • The Geochemical atlas the Data Base • The experience gained • The collaborations shaped

Applications and use

• Help industry stakeholders in locating resources (Mining industry, Cement industry ) • Help environmental stakeholders in identifying pollution. (eg arsenic GWB pollution in Mammari area) • Giving expert opinion on issues of regeneration of contaminated sites (Limni regeneration).

• Mari explosion area. Damage assessment and soil impact.

Finally…Acknowledgements

UNSW and co-workers team Prof David Cohen Dr Neil Rutherford Extensive assistance to the project was provided by the partner organisations, including Mr Andreas Demetriades (ADCS) Mr John Arneil (UNSW Global Consulting) Mr Amber Ahuja UNSW Global Consulting GSD team The project was supported and guided by the members of the project committee Mr Christos Christofi Mr Efthimios Tsiolakis Ms Eleni Demetriou (State General Laboratory) For valuable contributions to scientific, technical and logistical issues during the implementation phase of the Geochemical Atlas project Dr George Petrides Dr Polis Michaelides, former directors of the GSD, Dr Iain Dalrymple and Dr Eric Hoffman of Actlabs in Canada and Australia. Dr Antonios Charalambides Dr Stelios Nicolaides Special thanks go to: Ms Zomenia Zomeni Mr Takis Tsindides (Department of Forests), Mr Giorgos Hadjigeorgiou, Dr Dora Chimonidou and Dr Panagiotis Dalias (Institute of Agricultural Research), Mr Andreas Televantos, Mr Christos Hadjiantonis (Department of Agriculture), Ms Eleni Stavrou, Dr Maria Hadjicosti Ms Constantina Kapodistria, and Mr Giorgos Georgiou (Department of Antiquities).

Dr Irene Christoforou, Mr Giorgos Christodoulou, Ms Georgia Kadi Mr Peppinos Terzis.