Calcium and Magnesium SilicateAn Alternative Choice for Liming Acid Soils

The 8th International Symposium on Plant-Soil Interactions at Low pHOctober 18-22, 2012 Bengaluru, India

© 2012 Harsco Corporation, All Rights Reserved.

Stephen R. Miranda: Global Market ManagerAgriculture & Professional Turf-Grass Management

Sarver, Pennsylvania USA

� Introduction to Harsco Metals & Minerals

� Introduction to AgrowSil™: Harsco’s Calcium and Magnesium Silicate Lime

Alternative & Silicon-Based Fertilizer

� Brief review of USA Acid Soil Conditions

� AgrowSil™ vs. Lime

� Soil pH Adjustment

� AgrowSil™’s Mode of Action

� Silicon – “A Plant Beneficial Substance”

� AgrowSil™ Supplies Silicon

� Silicon & Nutrient Availability

� Silicon and Metal Toxicity

� Silicon’s In- Planta Benefits

1

Presentation Outline

© 2012 Harsco Corporation, All Rights Reserved. 2

Harsco Global Business Platforms

�The world’s most complete global organization for highly engineered rental scaffolding, shoring, concrete forming and other access-related services. Operating at

approximately 200 sites in over 40 countries

�The world’s largest provider of on-site, outsourced services

to the global metals industries and environmentally-responsible, mineral-based products for a range of

commercial and industrial uses. More than 160 sites in 30

countries.

�Global railway track maintenance services and equipment

�Energy-efficient air-cooled heat exchangers, heat transfer equipment, and industrial grating products

Harsco Corporation (HSC) is a diversified, global industrial services and engineered products company serving major industries that are

fundamental to worldwide economic growth.

Global provider of agricultural and turf products as well as metals recovery and mill services.

• Stainless Services

• Metal Recovery

• AgrowSil®/AgroSilicio®

• EXCELLERATOR®

• Global – 30 countries

• 160 sites

Harsco Metals & Minerals: Who we are ?

3

U.S. largest producer of blasting abrasives and third largest manufacturer of roofing granules.

• Utility Services

• BLACK BEAUTY®

• Abrasives

• Roofing Granules

• National – 16 sites

Leading producer of specialty metallurgical additives used primarily by steelmakers in the refining of molten steel.

• Metallurgical Additives

• Briquettes

• Desulfurizers/Deoxidizers

• Analytical Support

• National - 2 sites

Delivering innovative, economic and green

solutions for mineral recovery.

Harsco’s Global Presence

4

USA – PA & KY

• Reclime renamed to AgrowSil™

• Begin Ag in 1993

•Plant beneficial nutrient– AAPFCO 2/12

(Assoc Amer. Plant Food Control Officials)

•Powder and Pelletized Formulations

France

•Mineral Matrix

Brazil

• AgroSilicio™

• Begin Ag in 2001

• Fertilizer & Soil Conditioner

• Crops = Sugarcane, Soy, Coffee

South Africa

•Camisil

•Crops = Sugarcane, Soy, Coffee

China

• Ful l Production Q1 2013

• Cucumbers 30% yield increase

• Tomatoes 30% yield increase

• Corn/Sorghum increased growth

• Soi l = high acid to alkaline soil

• Extensive Rice Testing

The Making of

In a proprietary

process metals are

removed from

Stainless Steel Slag &

an environmental y

friendly Calcium and

Magnesium silicate

product , Agrowsil ™

is made.

PRODUCT

5

Chemical Analysis

6

AgrowSil and Metals

Accumulation

7

8

Agrowsil TCLP Metals Data Table 2010

Lab:Microseeps, Inc.

Test Methods used:U.S. Environmental Protection Agency, 1987, Test Methods for Evaluating Solid Waste,

SW-846, 3rd ed., Office of Solid Waste and Emergency Response, Washington, DC.

n/e = none established

Antimony Arsenic Barium Cadmium Chromium Copper Iron Lead Manganese Mercury Molybdenum Nickel Selenium Silicon Silver Thallium Zinc

max max max max max max max max max max max max max max max

PA/EPA 0.15 0.25 0.125 2.5 25 7.5 0.125 2.5 0.05 4.375 2.5 1 Report Only 50

MIN 0.050 0.004 0.250 0.001 0.042 0.002 0.017 0.003 0.001 0.00100 0.120 0.002 0.011 2.8 0.050 0.100 0.002

MAX 0.050 0.050 0.640 0.050 0.170 0.050 1.000 0.075 0.100 0.00100 0.290 0.100 0.038 27 0.050 0.100 0.044

MEAN 0.050 0.030 0.428 0.030 0.104 0.035 0.679 0.034 0.028 0.00100 0.175 0.068 0.022 18.73 0.050 0.100 0.014

Total Metals (mg/kg)

Composite Test Antimony Arsenic Barium Cadmium Chromium Copper Iron Lead Manganese Mercury Molybdenum Nickel Selenium Silicon Silver Thallium Zinc

Number Date

A01-10 1/18/2010 0.050 0.007 0.530 0.001 0.170 0.050 1.000 0.050 0.002 0.00100 0.260 0.100 0.023 27 0.050 0.100 0.003

A02-10 2/5/2010 0.050 0.008 0.450 0.050 0.150 0.050 1.000 0.050 0.100 0.00100 0.140 0.100 0.011 5.6 0.050 0.100 0.007

A04-10 3/11/2010 0.050 0.012 0.640 0.001 0.160 0.050 1.000 0.050 0.001 0.00100 0.290 0.100 0.032 26 0.050 0.100 0.005

A05-10 3/19/2010 0.050 0.050 0.450 0.050 0.110 0.002 1.000 0.050 0.100 0.00100 0.130 0.100 0.014 2.8 0.050 0.100 0.004

A06-10 3/26/2010 0.050 0.010 0.440 0.001 0.096 0.009 0.017 0.050 0.018 0.00100 0.220 0.100 0.030 26 0.050 0.100 0.033

A07-10 4/2/2010 0.050 0.050 0.370 0.050 0.083 0.050 1.000 0.050 0.001 0.00100 0.130 0.100 0.025 26 0.050 0.100 0.002

A08-10 4/10/2010 0.050 0.004 0.380 0.050 0.085 0.005 0.059 0.003 0.006 0.00100 0.140 0.003 0.021 21 0.050 0.100 0.014

A09-10 4/17/2010 0.050 0.050 0.290 0.050 0.042 0.050 1.000 0.005 0.003 0.00100 0.120 0.006 0.019 11 0.050 0.100 0.009

A10-10 4/30/2010 0.050 0.050 0.430 0.050 0.084 0.050 0.041 0.006 0.005 0.00100 0.150 0.100 0.017 20 0.050 0.100 0.044

0.050 0.013 0.450 0.001 0.110 0.004 0.035 0.075 0.002 0.00100 0.210 0.100 0.038 25 0.050 0.100 0.021

A11-10 5/14/2010 0.050 0.050 0.450 0.050 0.090 0.050 1.000 0.005 0.001 0.00100 0.170 0.003 0.022 26 0.050 0.100 0.019

A12-10 6/11/2010 0.050 0.050 0.250 0.010 0.065 0.050 1.000 0.017 0.100 0.00100 0.140 0.002 0.011 8.3 0.050 0.100 0.002

numbers in red font represent a less than (<) number

Metal concentrations in potato tubers as affected by AgrowSil soil amendment.

AgrowSil Calcitic Lime

Metal Result Detection Limit (mg/kg) Result Detection Limit (mg/kg)

Arsenic <DL 3.742514 <DL 3.787878

Cadmium <DL 2.245508 <DL 2.272727

Total Chromium <DL 2.245508 <DL 2.272727

Copper 7.75449 1.497005 7.022727 1.515151

Lead <DL 7.485028 <DL 7.575754

Mercury <DL 0.07485 <DL 0.075757

Molybdenum <DL 7.485029 <DL 7.575757

Nickel <DL 3.742514 <DL 3.787878

Selenium <DL 13.0988 <DL 13.25757

Zinc 16.66167 2.245508 16.84848 2.272727

AgrowSil Calcitic Lime

AgrowSil's effects on potato yields. Soil Si

Avg # potatoes/plant

Avg wt/potato

(lb)

Total harvest wt.

Tons/acre 0-6"

AgrowSil 13 0.479 90 58.89

Calcitic Lime 12 0.448 78 48.90

Higher Yield of Baking

Potatoes

(increased size & quality)

Areas of Acid Soils in the

Continental United States of America

pH classifications pH values

Extremely acid < 4.5

Very strongly acid 4.5 to 5.0

Strongly acid 5.1 to 5.5

Medium acid 5.6 to 6.0

Slightly acid 6.1 to 6.5

Neutral 6.6 to 7.3

Mildly alkaline 7.4 to 7.8

Moderately

alkaline7.9 to 8.4

Strongly alkaline 8.5 to 9.0

Very strongly

alkaline> 9.0 10

Soil Order Dominant Minerals Weathering

Soil Si Weathering Sequence

Mollisols

Vertisols

Inceptisols

Alfisols

Ultisols

Oxisols

Feldspars, Vermiculites

Smectites

Smectites, Kaolinites

Kaolinites, Smectites

Kaolinites, Sesquioxides

Sesquioxides, Kaolinites

less

more

De

sili

cati

on

11

As a Lime

Replacement

12

LIMESTONE

(CaCO3) = 14 mg/l

Being, 6.78% more

soluble than the limestoneSource: Technical Bulletin nbr. 6, ANDA – National Association of Fertilizer Difusion

(CaSiO3) = 95 mg/l

> PERCOLATION

13

Why just Lime when you can AgrowSil®?

Spreading of AgrowSil®

15

‘s Mode-of-Action

Neutralization of H+ by CaSiO3 forms monosilicic acid

(H4SiO4)

CaSiO3 + H2O + 2H+ ���� Ca + + + H4SiO4

16

5.2

5.4

5.6

5.8

6

6.2

6.4

6.6

So

il p

H

Dolomitic Lime's effects on soil pH

during Alfalfa Growing Season 2010

pH 0-2" soil depth pH 2-6" soil depth pH 0-6" soil depth

5.2

5.4

5.6

5.8

6

6.2

6.4

6.6

AgrowSil's effects on soil pH during

Alfalfa Growing Season 2010

pH 0-2" soil depth pH 2-6" soil depth pH 0-6" soil depth

•AgrowSil™ reduced soil acidity at all soil depths more

effectively than Dolomitic Lime.•AgrowSil™’s effect on soil acidity was more sustained

during the growing season, particularly at the 0-2” depth.

Comparison of AgrowSil & Dolomitic

Lime in Reducing Soil Acidity

17

‘s Mode-of-Action

The advantages of replacing lime with CaSiO3 don’t stop

with just neutralizing soil acidity. 18

CaSiO3 + H2O + 2H+ ���� Ca + + + H4SiO4

19

This resilification process fixes aluminum in place which reduces reserve acidity…

CaSiO3 Mode-of-Action

Feb. 2012 Silicon Approved by AAPFCO

as a “Plant Beneficial Substance”

20

A “plant beneficial substance” is any substance or compound other than primary, secondary, and micro plant

nutrients that can be demonstrated by scientific research to be beneficial to one or more species of plants, when applied exogenously.

Agriculture & Turf Products

• Soluble Silicon Fertilizer Extraction Method Approved Feb. 2012

• SLV Method Accepted for Publication Jul. 2012 ( J. of AOAC Intl.)

• Multi-Laboratory Collaborative Study to begin Winter 2012

21

AAPFCO & AOAC International Certifications

Ability To Market Products as Silicon-Based Fertilizers

Comparison of Lime and AgrowSil during Soybean

Cropping in 2011

Lime AgrowSil

Soil pH 0-6" depth 6.5 6.4

Soil Si (ppm) 68.2 88.6

Tissue Si (ppm) 262.1 691.2

• Similar soil pH effects but…

• 23.0 % Increase in Relative Soil Si with AgrowSil™

• 62.1 % Increase in Relative Tissue Si with AgrowSil™

Corrects Soil Acidity While

Supplying Soil & Plant Available Silicon

22

Increased Silicon Concentration in Pumpkin Leaves

0.00%

0.05%

0.10%

0.15%

0.20%

0.25%

0.30%

0.35%

0.40%

CaCO3 CaSiO3

Adding AgrowSil™ drastically improved Si uptake!23

y = 1.1895x + 4.2638R² = 0.5719 P=<0.0001

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25 30

AA

Si

(pp

m)

CEC (meq/100g of Soil)

Correlation between Acetic Acid-extractable Soil Si (AA Si) Levels & soil CEC of 16

Different New Jersey Soils

Positive correlation between soil Si

levels and soil Cation Exchange

Capacity (CEC)

24

Silicon Increases P use efficiency with

or without P fertilizers

25

Excerpted from V.V. Matichenkov et al., EFFECT OF Si-RICH SLAG AND LIME ON P LEACHING IN

SANDY SOILS. Journal American Society of Sugarcane Technologists, Vol.22, 2002 pp. 9-15

Corn Tissue-Young Growth Stage-Correction of

Micronutrient (Zn & Mn) deficiency with AgrowSil™

26

Sufficiency range Control Pelletized-AgrowSil™

Calcium .21-1.0 % 0.54 0.56

Magnesium .21-.60 % 0.25 0.26

Phosphorus .25-.40 % 0.51 0.54

Potassium 1.7-2.5 % 3.42 2.93

Nitrogen 2.7-3.5 % 3.13 3.6

Sulfur N/A 0.21 0.31

Sodium N/A <.001 0.003

Boron 4-25 ppm 7.43 7.17

Copper 6-20 ppm 13.61 14.73

Iron 21-250 ppm 181 210.1

Manganese 20-150 ppm 13.11 34.94

Zinc 20-70 ppm 15.18 23.02

Silicon Unknown 0.02 % 0.05 %

Silicon’s In- Planta Benefits

27

28

Plant Silicon Uptake

• Silicon moves up

thru the xylem

via water

transpiration

• Accumulates as

silica gel

Increased Disease Resistance

29

AgrowSil™’s Effects on Winter Wheat Flag Leaf Necrosis

Treatment 27-Jun-2006 19-Jun-2007 30-May-2008

-------------------------% Necrosis -----------------------

Amendment

Limestone 18.7 7.9 9.8

AgrowSil™ 13.2 5.9 5.5

P>F 0.05 0.0001 <.0001 0.0005

Fungicide

No 16.6 6.9 7.6

Yes 15.3 6.9 7.7

P>F 0.05 0.0029 0.9551 0.8729

Amendment x Fungicide *

*No significant Amendment x Fungicide interaction at P<0.05

significance level.

HPLC analysis of SF5 from FII of non-inoculated and inoculated plants amended or not with silicon

0.0

0.2

0.4

0.6

0.0

0.2

0.4

0.6

0 40 45 50 55 0 40 45 50 55

0 40 45 50 55 0 40 45 50 55

Minutes Minutes

0.0

0.2

0.4

0.6

0.0

0.2

0.4

0.6

Momilactone A

Momilactone B

Si- Si-

Si+ Si+

46 min

47 min

non-inoculated

non-inoculated inoculated

inoculated

Source: adapted from

Rodrigues et al., 2004

Silicon Protects Against High

Temperature Stress

Photograph of creeping bentgrass exposed to high temperature.

Plants had been grown for 55 days at 20 °C , and then exposed to

a temperature of 35-40 °C under constant light and humidity for

20 days. The growth of creeping bentgrass applied silicon sources

was similar. However, most of the control plants grown 35 °C

above had died by day 20.

Source: adapted from Lijun, et. al. 2004.

Increased Density, Yields and Si Uptake

32

Response of Kentucky Bluegrass, Seeded to 16 Different

New Jersey Soils, Amended with either

Dolomitic Limestone or Calcium Silicate

Amendment Density

(DENPC)

Fresh

Yield (g)

Dry Yield

(g)

Leaf Tissue

Si (%)

Dolomitic

Limestone

3335 6.40 2.08 .42

Calcium Silicate 3443 7.09 2.33 .72

P>F0.05 0.0244 0.0004 0.0054 <0.0001

31 May 2012 Zacherls Farm

Cucumber

6 J

ul 2

01

2 G

rie

be

lD

air

y

So

ybe

an

s

Background 500 lb/acre banded pelletized Tisco AgrowSil

Foreground same rate calcitic limeTisco AgrowSil Soybean Plants are Taller and Darker Green

This is after a rain event following a (3-4 wk)drought

Peppers: Zachrel’s Farm 2012

AgrowSil® at 200 lb/a

No AgrowSil

Thank You!

Any Questions?

Delivering innovative, economic and green

solutions for mineral recovery.