1. shopping
2. resources
3. contests and freebies

New approach to sample preparation for GFAA,
ICP-OES and ICP-MS with Milestone UltraWAVE,
The Game Changer in microwave sample preparation
U
r
o
f
Sav
การเตรียมตัวอย่างแนวใหม่สำหรับ GFAA, ICP-OES และICP-MS
ด้วยเครื่อง Milestone UltraWAVE : พลิกโฉมการเตรียมตัวอย่างด้วย
เทคนิคไมโครเวฟแบบใหม่
e
Giulio Colnaghi
Milestone S.r.l.
Maximizing Productivity
Saving the Environment
5
th
SITHIPHORN SCIENTIFIC
& TECHNOLOGY CONFERENCE
9 - 10 August 2011
at Chulabhorn Research Institute Bangkok
Milestone UltraWAVE
The Game Changer in Microwave Digestion
11/07/2011
Our Milestones
11/07/2011
“We can’t solve problems
by using the same kind of thinking
we used when we created them.”
(Albert Einstein)
11/07/2011
-1-
UltraWAVE
11/07/2011
Greater Ease of Use
Increased Productivity
Lower Operating Costs
Higher Performance
11/07/2011
SRC Technology
(Single Reaction Chamber)
11/07/2011
-2-
SRC Technology
SRC = Single Reaction Chamber
•The microwave cavity is the reaction vessel
•All samples digested together, any combination in the same run
•Same temperature and pressure, regardless of sample type and weight
•Just use ordinary auto‐sampler vials
11/07/2011
SRC Technology
• 990 mL stainless steel reaction chamber
• 1500 W high microwave power
• Cavity shape designed to ensure optimum microwave distribution
• Direct microwave coupling
• 900 mL sealed TFM liner inside the chamber
11/07/2011
Single Reaction Chamber
11/07/2011
-3-
UltraWAVE
Performance and Control
11/07/2011
Reaction Sensors
11/07/2011
Reaction Sensors
• Built‐in temperature and pressure sensors
• Up to 300°C temperature
• Temperature sensor housed in a PTFE‐coated Tantalum thermowell
• Up to 199 bar pressure
• No need for a reference vessel
• No need for sensors plug‐in
11/07/2011
-4-
Temperature Profile
11/07/2011
Temperature and Pressure Control
• Same temperature in all vials
• Temperature reading in the water base load
• Same pressure in all vials
• Pressure reading by pressure transducer
11/07/2011
Traditional Microwave Digestion
Environmental Samples
11/07/2011
-5-
Traditional Microwave Digestion
Pharmaceutical Samples
11/07/2011
Traditional Microwave Digestion
Food and Feed Samples
11/07/2011
UltraWAVE
All Samples
11/07/2011
-6-
UltraWAVE
(B) Blank (1) Environment (2) Pharmaceutical (3) Food and Feed
11/07/2011
UltraWAVE
(B) Blank (S) Standard Reference Material (1) Environment (2) Pharmaceutical (3) Food and Feed
11/07/2011
Cooling
• Chamber cooled by closed‐loop water cooling system
• UltraWAVE chamber directly connected to a water chiller
• Sensor to continuously monitor and control the temperature of the stainless steel chamber to prevent over‐heating
11/07/2011
-7-
Fast Cooling
Just 12 minutes from 270°C to 80°C
11/07/2011
UltraWAVE Digestion Sequence
11/07/2011
Digestion Sequence
11/07/2011
-8-
Why the pressurization step?
• Cap for all vials
• Preventing solutions boiling
• Preventing cross contamination
11/07/2011
H2O P&T
11/07/2011
H2O P&T
Load pressure at room temperature
11/07/2011
-9-
H2O P&T
Load pressure at room temperature
235°C
11/07/2011
H2O P&T
Actual pressure at 235°C
Load pressure at room temperature
235°C
11/07/2011
H2O P&T
Actual pressure at 235°C
Load pressure at room temperature
235°C
11/07/2011
- 10 -
270°C
Gas Loading
Direct connection to Nitrogen cylinder
11/07/2011
Nitrogen Cylinder ‘Lifetime’
Typical cylinder volume
50 L
Typical cylinder pressure
200 bar
‘Usable’ pressure
160 bar
(40 bar load pressure)
8000 L
(50 L * 160 bar)
200
(8000 L/40 bar)
Total volume
Runs
11/07/2011
UltraWAVE Racks and Vials
11/07/2011
- 11 -
Racks and Vials
11/07/2011
Racks and Vials
Rack Positions
Vials Material
Vials Volume (mL)
4
Glass (disposable)
TFM
70
70
5
Glass (disposable)
Quartz
TFM
35 and 40
25 and 40
25
15
Glass (disposable)
Quartz
TFM
15
10 and 15
10
22
Glass (disposable)
Quartz
TFM
10
10
7
11/07/2011
Disposable Glass Vials
• Eliminate the cleaning step
• Inexpensive
• Reduce overall sample preparation time
11/07/2011
- 12 -
Blank evaluation
11/07/2011
Blank Comparison Test
• Glass, quartz and TFM vials have been used
• Glass were new, uncleaned. Quartz and TFM were soaked overnight in c.HNO3. • UltraWAVE test conditions: 4mL trace metal grade c.HNO3
ramp to 220deg.C in 15min, hold for 20min.
• Cool, dilute to 40mL with DIW.
• Measure solutions using Agilent 7500cx ICP‐MS.
Both digestion and analysis were carried out in non‐
cleanroom conditions
11/07/2011
Blank Comparison Data
Max conc. scale 100ppb. B, Na, Al, K, Ca observed in glass blank
11/07/2011
- 13 -
Blank Comparison Data
Conc. scale zoomed to 10ppb max. B, K at single figure ppb level in quartz and TFM
11/07/2011
Selection of Vial Material
• Disposable glass vials gives similar blank results to the TFM or
quartz vials, with the exception of:
–
–
–
–
–
100‐500ppb: Na, Si
~100ppb: B, K
~50ppb: Al
~10ppb: Ca
<5ppb: Mg
• However, except for B, most routine samples are high in these elements
Study demonstrates extremely low blanks achievable for large majority of elements – even with glass 11/07/2011
UltraWAVE User Interface
11/07/2011
- 14 -
User Interface
11/07/2011
Parameters
11/07/2011
Method
11/07/2011
- 15 -
System
11/07/2011
Run
11/07/2011
Video
11/07/2011
- 16 -
11/07/2011
Key Benefits
Greater ease of use
Increased productivity
Lower operating costs
Higher performance
11/07/2011
Greater Ease of Use
• Lower handling
• No vessel cap/uncap
• Direct temperature and pressure control in all samples
• Mixed batch samples in the same run
• One method for all samples
• Blanks and reference standards digestion alongside with samples
11/07/2011
- 17 -
Increased Productivity
•
•
•
•
•
Reduced labor costs
High sample throughput
No vessel assembly/disassembly
Fast cooling
Vessel cleaning is eliminated with disposable glass vials
11/07/2011
Lower Operating Costs
• Less labor
• Less reagents volume
• Relatively inexpensive vials
11/07/2011
Higher Performance
• Temperature 300°C
• Pressure 199 bar
• High sample amount
• Low blanks
11/07/2011
- 18 -
UltraWAVE productivity
11/07/2011
Productivity comparison
HDPE polymer
Traditional microwave Closed Milestone UltraWAVE
vessel
12 positions rotor* have been used.
15 positions rack
High temperature and pressure will be achieved so high pressure rotor must be used
N°2 rotors are used to increase the productivity. N°2 racks are used
2nd rotor is load during thdigestion run
2nd rotor is load during thdigestion run
* 40 positions rotors are available but cannot be used for polymer digestion
11/07/2011
Run time comparison
HDPE polymer
Closed Vessel
With 12 Position High Pressure Rotors
UltraWAVE
With 15 Position Racks Weigh 12 samples, add acid, assemble vessels, load into rotor
24min
Weigh 15 samples, add acid and cap, place vial in rack 10min
Microwave program: 20min to 210 deg.C, hold for 20min 40min
Microwave program: 10min to 210 deg.C, hold for 20min 30min
Cool down to 65 deg.C
20min
Cool down to 65 deg.C
15min
Vessel disassembly
12min
Vessel disassembly
N/A
Total run time
96min
Total run time
55min
Subsequent runs
(load 2nd rotor during previous run)
72 min
Subsequent runs (load 2nd rack during previous run)
45min
Number of runs in an 8 hour shift
6.3
Number of runs in an 8 hour shift
10.4
Samples digested in an 8 hour shift
76
Samples digested in an 8 hour shift
157
11/07/2011
- 19 -
Productivity comparison
Plant material
Traditional microwave Closed Milestone UltraWAVE
vessel
24 positions rotor* have been used.
15 positions rack
Lower temperature and pressure will be achieved, so medium pressure rotor can be used
N°2 rotors are used to increase the productivity. N°2 racks are used
2nd rotor is load during thdigestion run
2nd rotor is load during thdigestion run
* 40 positions rotors are available but they are rarely used at full capacity
11/07/2011
Run time comparison
Plant material
Closed Vessel
With 24 Position High Capacity Rotors
UltraWAVE
With 15 Position Racks
Weigh 24 samples, add acid, assemble vessel, load into rotor
35min
Weigh 15 samples, add acid and cap, place vial in rack 10min
Microwave program: 20min to 180 deg.C, hold for 10min 30min
Microwave program: 10min to 180 deg.C, hold for 10min 20min
Cool down to 65 deg.C
30min
Cool down to 65 deg.C
12min
Vessel disassembly
15min
Vessel disassembly
N/A
Total run time
110min
Total run time
42min
Subsequent runs
(load 2nd rotor during previous run)
75min
Subsequent runs (load 2nd rack during previous run)
32min
Number of runs in an 8 hour shift
6
Number of runs in an 8 hour shift
14.7
Samples digested in an 8 hour shift
144
Samples digested in an 8 hour shift
220
11/07/2011
Samples Digested in one working day
(8 hours)
HPDE Polymer
Closed vessel 12 pos. rotor
76 samples
157 samples
UltraWAVE 15 position rack
Plant Digests
144 samples
Closed vessel 24 position rotor
UltraWAVE 15 position rack
220 samples
The UltraWAVE is more productive than closed vessel digestion with a 24
position rotor – even when the UltraWAVE is digesting polymers
- 20 -
Applications
11/07/2011
Conventional microwave Vs UltraWAVE
Vessel Volume
Maximum pressure
Cooling
Pressure developed
Conventional microwave
UltraWAVE
Up to 100 ml
900 ml
100 bar
199 bar
Digestion of higher sample amount
Air
Water cooling
Higher temperature for long time and faster cooling
By acid vapor pressure and by Vessel pressurized with inert sample decomposition
gas, preventing solution boiling
Temperature and pressure of Samples can be at different T Samples are at the same T and P
the vessels
and P
11/07/2011
High Sample Amount
5‐position rack with 3 g food samples @ 250°C
8 ml of HNO3 and 2 ml of H2O2
11/07/2011
- 21 -
Difficult Samples
5‐position rack with 0,1 g SiC samples @ 280°C
3 ml of H2SO4, 3 ml of HNO3 and 3 ml of HF
11/07/2011
Method Development Guidelines
11/07/2011
Vessel Load
120 mL H2O and 5 mL H2O2
•Uniform heating rate and temperature across digestion vials
•Slowing down exothermal reactions
11/07/2011
- 22 -
Pressure Load
• Cap for all vials
• Preventing solutions boiling
• Preventing cross contamination
11/07/2011
H2O P&T
Actual pressure at 235°C
Load pressure at room temperature
235°C
270°C
11/07/2011
Pressure Setting
50 bar
Very reactive samples, generating elevated pressure (organics such as polymers, oils…)
40 bar
Moderately reactive samples (organics such as food, feed, biological…)
30 bar
Non‐reactive samples (inorganics such as rocks, minerals…)
11/07/2011
- 23 -
Organics
Food, feed, plants, polymers, oils…
11/07/2011
Organics
Organics + HNO3
MeNO3 + CO2 + NOX + H2O
•Exothermal reactions
•Large pressure is generated
•Typical temperature 180‐240°C
– A higher temperature may be required depending on sample matrix and digestion goal
11/07/2011
Reagents
• 5 parts HNO3 1 part H2O2
Rack
4
5
15
22
Total volume (mL)
10
8
4
3
11/07/2011
- 24 -
Sample Amount
• Dry organic material
Rack
4
5
15
22
Amount (g)
> 3,0
1,0‐3,0
0,1‐1,0
< 0,1
11/07/2011
Temperature Profile
15‐position rack with 1,0 g fresh meat @ 220°C
5 ml of HNO3 and 1 ml of H2O2
11/07/2011
Temperature profile
5‐position rack with 4g dry food @ 220°C
Totally 20g of organic sample!!!
11/07/2011
- 25 -
Inorganics
Rocks, metals, ceramics, refractories…
11/07/2011
Inorganics
• Not excessive pressure
– Typical sample amount 0,1‐1,0 g
• Choice of reagents is critical
– For example 5 parts HF and 1 part HNO3
• Require relatively high temperature (up to 280°C) and long digestion time
11/07/2011
Temperature Profile
15‐position rack with 0,1 g silica sand @ 240°C
5 ml of HF and 1 ml of HNO3
11/07/2011
- 26 -
Heterogeneous Samples and Batches
11/07/2011
Heterogeneous Samples and Batches
• Select the correct start pressure referring to the most reactive sample
• Set the target temperature of the most difficult sample
• Slow temperature ramping when organics are present
11/07/2011
Application Examples
11/07/2011
- 27 -
Food and Feed
• Milk powder (UW‐1)
• Fresh food or feed (UW‐
18)
• Dry food or feed (UW‐
19)
11/07/2011
Consumer Products
• Toys (UW‐2)
• Polyethylene (UW‐11)
• Textile (UW‐17)
11/07/2011
Toys
22 position rack with glass vials
11/07/2011
- 28 -
Environmental
• US EPA 3051 (UW‐14)
• US EPA 3052 (UW‐15)
11/07/2011
Others
•
•
•
•
•
Blue ink (UW‐5)
Carbon fiber (UW‐12)
Silica sand (UW‐13)
Biological (UW‐20)
Fuel oil (UW‐21)
11/07/2011
Recovery study
11/07/2011
- 29 -
Milestone DMA‐80
11/07/2011
UltraWAVE rack
11/07/2011
Digestion profile
11/07/2011
- 30 -
Results
11/07/2011
Cross contamination study
11/07/2011
Cross Contamination Study
- 31 -
11/07/2011
Olive Leaves
•
•
•
•
Sample weight 500 mg
Reagent 5 mL HNO3
Digestion time 20 minutes
Maximum temperature 220°C
• Maximum pressure 150 bar
• Glass vials*
11/07/2011
Olive Leaves
Element
UltraWAVE
ETHOS One (Average)
P
1.530
1.400
K
12.602
13.100
Ca
21.589
23.950
Mg
1.917
2.043
B*
210,5
201,5
Fe
88,2
88,5
Mn
28,2
26,0
Cu
31,3
33,6
Zn
18,5
17,9
Results in mg/kg
11/07/2011
- 32 -
11/07/2011
Grapes Tree
•
•
•
•
Sample weight 500 mg
Reagent 5 mL HNO3
Digestion time 20 minutes
Maximum temperature 220°C
• Maximum pressure 150 bar
• Glass vials*
11/07/2011
Grapes Tree
Element
UltraWAVE
ETHOS One (Average)
P
941
929
K
7.657
7.644
Ca
5.443
5.251
Mg
1.066
1.020
B*
129,9
79,0
Fe
19,0
31,0
Mn
26,0
26,0
Cu
11,3
13,0
Zn
20,7
20,7
Results in mg/kg
11/07/2011
- 33 -
11/07/2011
Apple Leaves
•
•
•
•
Sample weight 500 mg
Reagent 5 mL HNO3
Digestion time 20 minutes
Maximum temperature 220°C
• Maximum pressure 150 bar
• Glass vials*
11/07/2011
Apple Leaves
Element
UltraWAVE
Ring Test (Average)
P
2.687
2.600
K
21.890
20.400
Ca
8.831
8.300
Mg
2.051
1.900
B*
70,1
35,9
Fe
102,9
94,3
Mn
89,3
75,5
Cu
7,2
10,2
Zn
45,1
43,1
Results in mg/kg
11/07/2011
- 34 -
11/07/2011
Hay
•
•
•
•
Sample weight 500 mg
Reagent 5 mL HNO3
Digestion time 20 minutes
Maximum temperature 220°C
• Maximum pressure 150 bar
• Glass vials*
11/07/2011
Hay
Element
UltraWAVE
Ring Test (Average)
P
1.382
1.401
K
14.202
14.630
Ca
4.999
4.772
Mg
1.244
1.213
Fe
268,3
222,0
Mn
41,9
38,0
Cu
5,9
6,1
Zn
361,2
346,0
S
1.434
1.422
Se
0,036
0,028
Mo
1,32
0,99
Cd
2,18
1,97
Results in mg/kg
11/07/2011
- 35 -
Milestone Laboratory
11/07/2011
Thank You!
11/07/2011
- 36 -