phosphorus flagship for stewardship

Phosphorus a flagship for stewardship: Challenges facing India today, global reserves, opportunities

for nutrient recycling, use efficiency and P-footprint

Abhijit Sarkar Roll No. 10532

Division of soil Science & Agricultural Chemistry Indian Agricultural Research Institute

New Delhi - 110012

CONTENTS

Stewardship:

“responsibility for sustainable

development shared by all those

whose actions affect environmental

performance, economic activity, and

social progress, reflected as both a

value and a practice by individuals,

organisations, communities and

competent authorities.”

International Standard Organization

(ISO 20121) HMS Victory, flagship of the First Sea

Lord of the Royal Navy

Flagship:

A vessel used by the commanding

officer of a group of naval ships,

reflecting the custom of its

commander, characteristically a flag

officer, flying a distinguishing flag.

Introduction

P N Fe C

Limiting nutrient

“The nutrient present in the least relative amount is the limiting nutrient”

The Barrel concept

“even if all but one of the essential elements be present, the absence of that one constituent renders the crop barren”

Liebig’s Law of Minimum

Phosphorus use efficiency not more than 20%

Phosphorus, a limiting nutrient………..Why?

Al3+ Fe3+

Fe3+ Al3+

H2PO4-

AlPO4. 2H2O

FePO4. 2H2O

Ca3(PO4)2 HPO42-

Ca2+

Ca2+

Ca2+

Ca2+

Ca2+

P P

P P

Phosphorus, a limiting nutrient………..Why?

Why is phosphorus (P) so important for living body ?

P is structural component of Adenosine tri-phosphate

(ATP) and Adenosine di-phosphate (ADP).

Processes and functions of ATP and ADP in plants

Membrane transport

Cytoplasmic streaming

Photosynthesis

Protein biosynthesis

Phospholipid biosynthesis

Nucleic acid synthesis

Generation of membrane electrical potentials

Respiration

Biosynthesis of cellulose, pectins, hemicellulose, and

lignin

Lipid biosynthesis

Isoprenoid biosynthesis; steroids and gibberellins

Fundamentals of Soil Science (2009)

Why is rock phosphates (RPs) so important for living body ?

ROCK PHOSPHATE

IFDC (2010)

Limitation confronting India for enhancing her agricultural produce

India as a country having 1.22 billions population but endowed with about 2.4% share of the continental land mass

Has limited land tract not commensurate to the need of the seething mass of humanity settled within the confines of the national boundary

Consequently the country would need in foreseeable future extensive application of NPK fertilizer in a balanced form for enhanced food production

Fortunately the arable land mass of the country is however not so insignificant

Rock phosphate therefore would remain as an essential fertilizer raw material input for sustaining the ever increasing food security of the nation

Unfortunately India as a country with sub-continental dimension has very limited phosphate mining operation

http://agricoop.nic.in/

Resource :

A concentration of naturally occurring phosphate material in such

a form or amount that economic extraction of a product is

currently or potentially feasible.

Reserve Base:

The part of an identified resource that meets minimum criteria

related to current mining and production practices including

grade, quality, thickness and depth.

Reserves:

The part of the reserve base which can be economically extracted

or produced at the time of the determination (this does not signify

that the extraction facilities are in place or functional).

Economic:

Profitable extraction or production under defined investment

assumptions has been established, analytically demonstrated or

assumed with reasonable certainty.

Definitions…..

IFDC (2010)

World phosphate reserves and resources of Marine phosphorite (Sedimentary phosphate rock, in mmt of material containing at least 30% P2O5)

IFDC (2010)

World phosphate reserves, resources and production of Apatite of Igneous origin (in mmt of material containing at least 30% P2O5)

Overall phosphate (sedimentary & igneous origin) reserves, resources and production in present scenario

IFDC (2010)

World phosphate rock reserve

United States Geological Survey, Mineral Commodity Summaries (January 2012)

71,000 (mmt)


World rock phosphate reserves

Morocco/ Western

Sahara

70%

Iraq

8%

China

5%

Algeria

3%

Syria

3%

Jordan

2%

South Africa

2% USA

2%

USSR

2% Brazil

0%

Australia

0%

Peru

0%

Israel

0%

Senegal

0%

Egypt 0%

Tunisia

0%

Others

1%


World rock phosphate reserve Contd…

Major rock phosphate reserve in India and their properties

Mussoorie RP

Total P % 8.25

WSP % 0.001

CSP % 1.19

CSIP % 7.06

Ca % 12.1

Udaipur RP

Total P % 8.62

WSP % 0.002

CSP % 1.26

CSIP % 7.36

Ca % 6.4

Jhabua RP

Total P % 7.25

WSP % 0.003

CSP % 1.10

CSIP % 6.15

Ca % 9.96

Purulia RP

Total P % 9.87

WSP % 0.004

CSP % 1.25

CSIP % 8.62

Ca % 7.8

240 million tonnes

(Mt) of RP deposits

are available in India

and

About 5.11 Mt meets

the specification of

the fertilizer industry


Phosphorus footprint The Phosphorus footprint is the accounting methodology framework for

creating a quantified flow chart

Phosphorus declaration illustrates the losses and management improvement

possibilities.

The removal and reuse of phosphorus is the most significant consideration

for wastewater treatment facilities

It is estimated that wastewater contributes approximately 1.5 Tg/yr to the

global phosphorus footprint which is at least 10% of the total based on the

largest estimate for the global phosphorus footprint

Anonymous (2009)

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

No P removal P removal 0.1(mg /L)

P removal 1(mg /L)

P recovery

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Eutrophication Phosphorus

Phosphorus footprint

Anonymous (2009)

What is phosphorus recycling?

Phosphorus recycling

Fundamentals of Soil Science (2009)

Watery phase: wastewater (treated) or process water (e.g. sludge liquor)

Crystallization DHV-Crystalator (Giesen and Boer, 2003)

Unitika PHOSNIX (Uneo and Fujii, 2001)

Ostara PEARL (Esemag, 2006)

CSH-process Darmstadt (Petzet, 2009)

P-ROC–process (Berg, 2005)

Precipitation AirPrex (Heinzmann, 2008)

Prisa-process (Pinnekamp and Montag, 2007)

Dewatered (or dried) sewage sludge

Wet chemical

Thermal

Seaborne-process or Gifhorn-process (Muller, 2005)

Mephrec-process, (dried sludge) (Scheidig et al., 2009)

Sewage sludge ash

Wet chemical

Thermal

BioCon-process (Hultman et al., 2003)

SEPHOS process (Cornel and Schaum, 2005)

PASCH process (Montag et al., 2005)

ASH DEC process (Adam, 2009)

Electro thermal P (Cornel, 2002)

Anonymous (2009)

Processes for phosphorus recovery from non-conventional sources

Processes for phosphorus recovery from low graded rock phosphates (RPs)

Partial acidulation of low graded RPs (Stephan and Condron, 1986;

Hammond et al., 1986)

Compaction of RPs with soluble phosphates (Menon and Chien, 1996;

Begum et al., 2004)

Mobilization of RPs phosphorus using fresh cow dung and pyrite

(Biswas et al., 1996)

Mixing of RPs with elemental sulphur (Basak et al., 1987)

Enhanced Biological P Removal (EBPR) process (Sedlak, 1991)

Aspergillus spp.

Phosphorus recovery from municipal solid waste incineration (MSWI) fly ash

Ash leaching

pH <1 1st precipitation

pH = 3

2nd precipitation

pH = 4

leachate filtrate

Residual filtrate

Ash residues Fe rich solids Solid P product

MSWI

ash

2 M NaOH 1 M NaOH 2 M HCl

Ash leaching

pH=4

Alkaline leaching

pH=(11-13)

Ash residues

with P

P rich filtrate

Ca rich leachate Ash residues

MSWI

ash

1 M NaOH 1 M HCl

Recovery Method 1: Acidic leaching and precipitation

Recovery Method 2: Two step acidic alkaline leaching

Kalmykova and Fedge (2013)

Average concentration of P (mg L-1) detected in leachates


Ash particle size 50-950 µm (median value 340 µm)

Initial P content 5.9 g kg-1

Ca (141 g kg-1),

Fe (19 g kg-1),

Al (32 g kg-1)

P leaching efficiency (%) or PE (%)

PE (%)=𝑷𝒍𝒆𝒄𝒉𝒂𝒕𝒆

𝑷𝒂𝒔𝒉

∗ 𝟏𝟎𝟎

Overall P recovery efficiency (%) or REP(%)

REP(%) =𝑴𝑷𝒔𝒆𝒄𝒐𝒏𝒅 𝒑𝒓𝒆𝒄𝒊𝒑𝒊𝒕𝒂𝒕𝒊𝒐𝒏

𝒎𝑷𝒍𝒆𝒄𝒉𝒂𝒕𝒆

∗ 𝟏𝟎𝟎


Contd……

Other,

Mainly

oxygen, 55%

Cl, 17%

Al, 8%

Fe, 4%

Na, 3%

H, 3%

P, 3% S, 2%

K+Ca, 2% Zn, 1% Other

metals,

2%

Composition (% wt) of low grade phosphate ores compared to the obtained P product


Method I: P recovery efficiency 70%

Final product contains 3% P

Trace metal content excessively high

Method II: P recovery efficiency <1%

High Ca content in final product

Potentially more pure P obtained


Contd……

Rock phosphate (RP) enriched compost: An approach to improve low-grade Indian rock phosphate

Rock phosphate enriched composts (RP-compost):

prepared by mixing four low-grade Indian rock phosphates with rice

straw with and without Aspergillus awamori

Mix ground RP @ 2 and 4 kg P (elemental P basis) per 100 kg of air-

dried rice straw (corresponding to 2% and 4% charged rate) with and

without phosphate solubilizing microorganism (PSM) viz. A. awamori

(@ 50 g per 100 kg of rice straw)

To enhance activity of the natural and added microflora, a uniform dose

of urea solution @ 0.25 kg N per 100 kg of rice straw was sprayed.

Fresh cow dung @ 5 kg per 100 kg of rice straw was made into slurry

and sprinkled to each treatment as natural inoculums.

A uniform dose of Trichoderma viride was inoculated @ 50 g per 100 kg of rice straw (on fresh mycelia weight basis) to hasten the composting.

mixed thoroughly, moisture content maintain 50-60% of field capacity

Duration 120-130 days

Biswas and Narayanasamy (2006)

Processes for phosphorus recovery from low graded rock phosphates (RPs)

Biswas and Narayanasamy (2006)

Effect of mineral elements on phosphorus release from heated sewage sludge

Laboratory activated sludge (L Sludge) and

wastewater treatment plant activated sludge

(WTP sludge)

Heated samples, centrifuged at 8000 rpm for 5

mins.

For P precipitation, CaCl2 was added to

supernatant solution, to maintain stoichiometric

Ca : P of 1:1 (pH 11)

Incubated for 2 hours at room temperature and centrifuged at 8000 rpm for 5 mins

Sludge samples heated at 70°C for 1 hour on a

water bath

Takiguchi et al. (2007)

Influence of addition mineral salts on the phosphorus release from the L-sludge

* - 0.01 level,

** - 0.05 level

Control

Organic phosphorus

Inorganic phosphorus

Residual phosphorus

Each salt was added to the L-sludge @ 5 mM before heat treatment


Dependency of phosphorus release on the total concentrations of Al, Mg, and Ca in WTP sludge


Phosphorus recovery from sewage sludge char ash

Anaerobically digested and thermally dried sewage sludge

(Butarque & Madrid Sur)

Grinding and sieving

(particle diameter 250-500 µm)

Pyrolysis

(Fluidized bed reactor 530°C)

Char Non-condensable gasses Pyrolysis liquid

Combustion

(Muffle furnace 600-900°C) Gasification

(Fluidized bed reactor 820°C)

Ash Gas Water + Tar Ash

Martinez et al. (2014)

P yield % =Plechate

Pash

∗ 100

Phosphorus yield (%) after leaching sewage sludge pyrolysis char ash with H2SO4

Phosphorus yield (%) after leaching sewage sludge pyrolysis char ash with oxalic acid

Martinez et al. (2014)

Benefits of phosphorus recovery and reuse

Cordell (2010)

Term Description Refferences

Agronomic PUE Yield increase per unit P applied Hammond et al., 2009

P use efficiency (I) Grain yield per nutrient supplied Manske et al., 2001

P use efficiency (II) Shoot biomass per unit P uptake Wissuwa et al., 1998

P uptake efficiency (I) Total above ground nutrient per unit P applied Osborne and Rengel 2002a

P uptake efficiency (II) Total P accumulated per unit root weight and length Liao et al., 2008

P acquisition efficiency Total P in the plant per unit P applied Osborne and Rengel 2002a

P utilization efficiency Grain yield per unit P uptake Manske et al., 2002

Shoot P utilization efficiency (I) Shoot biomass per unit P uptake Su et al., 2006

Shoot P utilization efficiency (II) Shoot biomass per unit P uptake (shoots and roots minus

seed P reserve)

Osborne and Rengel 2002a

Biomass utilization efficiency Biomass yield per unit P uptake Su et al., 2009

P harvest index Grain p concentration per total P uptake Batten 1992

P efficiency ratio (I) Grain yield per unit P uptake Jones et al., 1989

P efficiency ratio (II) Shoot growth at low P relative to shoot growth at high P Ozturk et al., 2005

Relative grain yield Grain yield at low P relative to grain yield at high P Graham 1984

Root efficiency ratio P uptake in tops per unit root dry weight Jones et al., 1992

Phosphorus use efficiencies and its synonymous

Bovill et al. (2013)

Possible mechanisms of P acquisition and utilization for better growth of modern crop

Bovill et al. (2013)

Richardson et al. (2011)

Plants and microbial strategies to improve the phosphorus efficiency in agriculture

There are three general strategies that triggers large increase in P

acquisition

Strategy 1: “Root foraging strategies”

Lower the critical P requirement for plant growth

Agriculture to be operated at lower plant available P

concentration

Slow the rate at which P accumulates in moderate to high P

sorbing soils

Strategy 2: “Soil P mining strategies”

Enhance the desorption, solubilisation or mineralization of P

from sparingly available pool and slowly mineralizing or

resistant organic P pool in soil

Strategy 3: Development of transgenic plants through molecular assisted

plant breeding and biotechnology

Strategy 1: Root foraging strategies, improve acquisition of soil P

1. More & longer adventitious root

2. More horizontally oriented basal roots

3. More taproot laterals

4. More dispersed higher order laterals

5. Increased root hair density and length

6. Greater association with mycorrhizae

7. Greater formation of aerenchyma

Plant mechanisms for improving phosphorus acquisition efficiency

Ramaekers et al. (2010)

Strategy 1: Root foraging strategies (Root hair structure and distribution in surface soil) contd…

Shallower root growth angles of

axial roots (basal roots in

legumes and crown and seminal

roots in cereals)

enhanced adventitious roots

better dispersion of lateral

roots


Strategy 1: Root foraging strategies (Root hair structure and distribution in surface soil) contd…

Crop: Phaseolus vulgaris

Soil type:

Oxisol (order), Udox (sub-order)

Red loam soil

pH- (4.5-5.5)

Miguel et al. (2015)

Strategy 1: Root foraging strategies (Root hair length and mycorrhizal association) contd…

Mycorrhizal association


Effect of arbuscular mycorhizal fungi and added phosphorus on fruit yield of chilli

Inoculation

Yield of chilli (kg pot-1)

Addition of P fertilizer

No addition Half the recommended

level

Recommended level

(75 kg ha-1)

Uninoculated 0.27 0.37 0.43

Glomas fasiculatum 0.40 0.52 -

Glomas albidum 0.38 0.42 -

Glomas macrocarpum 0.32 0.40 -

Glomas caledonicum 0.37 0.41 -

The efficiency of P uptake by AMF has been related to both the spatial

distribution of the AMF extraradical hyphae in the soil and to the capacity of P

uptake by unit length of the hyphae.

Calculations have shown that hyphal inflow of P (uptake per unit length of hyphae

per unit time) is around 18 x 10–14 mol cm–1 s–1 or about six times more compared

to non-mycorrhizal roots.

Soil: Alfisol, loamy soil, Crop: Chilli

Bagyaraj et al. (2015)

Strategy 1: Root foraging strategies (formation of root cortical aerenchyma) contd…

Root cortical aerenchyma

(RCA) and delayed secondary

development are important for

P acquisition as they regulate

the root costs.

Root cortical aerenchyma are

formed under nutrient stress

and oxygen stress conditions.

Root cortical cells died and

filled by air to form

aerenchyma.

Reduce nutrient and carbon

costs of root tissue while

maintaining surface area for

nutrient uptake.

LP= root weight under low P concentration

HP= root weight under high P concentration

Normal root Root cortical aerenchyma


Strategy 2: Soil phosphorus mining strategies

Mechanisms of phosphate solublization or phosphorus mining strategies:

Organic acids:

• PSM is generally accompanied by a decrease in pH of the medium

• Analysis approve the presence of organic acids e.g.- lactic, citric,

glycolic, succinic, malic, oxalic, fumaric acid etc. (Vassilev et al., 1996).

Chelating substances:

• 2-ketogluconic acids causes P release from insoluble phosphates by

chelation mechanism

• Chelation of Ca by oxalic acid also helps in the solublization of

insoluble phosphates (Illmer and Sachinner, 1992).

Humic substances:

Humic, Fulvic acids are strong chelating agents that efficiently chelate

significant amount of Ca2+ and release H+ ions thus creating a driving

force for dissolution of insoluble phosphates (Singh and Amberger, 1990).

Enzymes and phosphorus solublization:

The liberation of P from organic phosphate compounds may be due

the action of enzymes of esterase type

Production of H2S:

Sulphate reducing bacteria (anaerobic condition) produce hydrogen

sulphide which can solubilize ferric phosphates by forming insoluble

sulphides of iron and making P soluble

Heterotrophic microbes also produce H2S which help solublization of

ferric phosphates by reducing it to ferrous sulphide with the release

of available phosphates (Gaur, 1990).

Production of CO2:

Respired CO2 reduce the pH due to formation of H2CO3 that increase

the availability of phosphates and subsequent uptake by plants (Hayman, 1975).

Production of mineral acids:

Sulphur oxidizing bacteria produce mineral acids (e.g.- H2SO4) during

oxidation of reduced sulphur containing compounds e.g.- pyrite,

which causes dissolution of insoluble phosphate rock, and release P

Pyrite + molecular oxygen Iron sulphate

Iron sulphate + H2O H2SO4

H2SO4 2H+ + SO42-


contd…

( Kapoor et al., 1991).


contd…

Production of siderophores:

Siderophores (Greek: "iron carrier") are small, high affinity iron

chelating compounds secreted by micro-organisms such as bacteria,

fungi and grasses

Siderophore Organism

Enterobactin Escherichia coli

Bacillibactin Bacillus subtilis

Bacillus anthracis

Vibriobactin Vibrio cholerie

Catecholate siderophores

Phytoiderophore Organism

Ferrichrome Ustilago sphaerogena

Desferrioxamine B Streptomyces pilosus Streptomyces coelicolor

Desferrioxamine E Streptomyces coelicolor

Fusarinine C Fusarium roseum

Ornibactin Burkholderia cepacia

Hydroxamate phytosiderophores

epi-hydroxymugineic acid Deoxymugineic acid

Mugineic acid

Römheld and Marschner (1990)

Phosphorus mining micro-organisms

Historical and future sources of phosphatic fertilizers

Cordell (2010)

Peak Phosphorus

Controlled release phosphatic fertilizer: a novel concept for increasing phosphorus use efficiency

Controlled-release fertilizers (CRF) are made to release their content of

nutrients gradually and if possible to coincide with the nutrient

requirements of a plant.

These fertilizers are prepared by coating the active soluble component

with a membrane that serves as a diffusion barrier

The rate of nutrient release has frequently been controlled by the slow

diffusion of the nutrient ions through the membrane to the soil

Phosphatic

fertilizer H2O Phosphatic

fertilizer

H2PO4-

H2PO4-

H2PO4-

H2PO4-

H2PO4-

H2PO4-

H2PO4-

Phosphatic

fertilizer Phosphatic

fertilizer

H2PO4-

H2PO4-

H2PO4-

Shrink your phosphorus footprint: How?

Say no to excess and unbalanced

fertilization

Use phosphate free laundry detergent

Plant a buffer strip along the margin of

water body

No soaps in water

Controlled roof runoff

Have a soil erosion consultation

Scoop the poop of pets

Boat responsibly

No tri-sodium poly phosphate

Anonymous (2009)

Tackling the

P suitability

challenges in

India

Business Development

Awareness rising

Development of Indian policies

Knowledge transfer

Research & Development

Smart co-operation

Incentives & targets

How to tackle the P sustainability challenges in India?


Technology implementation

Dynamic modelling

Scenario analysis

Cost-Benefit analysis

Indicators and P-footprints

Spatial distribution

Soil accumulation

Eutrophication

Waste management

Industrial transition

Process efficiency

Recycling technology

Chemical interaction

Fertilization experiments

Soil processes

Defining research agenda for sustainable P management through the integration of the macro-, meso-, and micro-

scales of research and knowledge


5R Strategies to reduce India’s dependency on phosphate rock derived P


Conclusions Phosphorus is an essential component for crop growth-development

and yield, thus acts as a flagship.

Conventional source of P is non-renewable, so nutrient (P) must be

recycled from waste water that contributes more than 10% of world

phosphorus footprint.

RP-compost could be an alternative and viable technology to utilize

both low-grade rock phosphates and rice straw efficiently and could be

used successfully as a cheaper source of P-fertilizer in place of costly

water soluble P like diammonium phosphate in crop production.

Heat treatment, pyrolysis of sewage sludge is an alternate method for

using non-conventional sources of P.

Plant having better root proliferation with root cortical aerenchyma, and

lesser basal root growth angle have better phosphorus utilization

efficiency

Slow release phosphatic fertilizers that synchronize the nutrient release

in accordance with plant demand is the newest concept for

improvement of plant phosphorus use efficiency

Future way….

Thank you…….

0

0.5

1

1.5

2

2.5

3

3.5

1990s 2000s Current

Population Growth Rate Foodgrain Production Rate

%

Population growth rate and food grain production rate in India

Food insecurity

phosphorus flagship for stewardship

Education