Underwater mass spectrometers to monitor coastal waters, harbors ...

Real-time Monitoring of Aquatic Environments with
an Underwater Mass Spectrometer
Peter G. Wenner, F.H.W. van Amerom, S.K. Toler, J.E. Edkins,
K. Koehn, R.J. Bell, M. Hall and R.T. Short
University of South Florida Center for Ocean Technology

USF/COT Underwater Mass Spectrometry Program
First generation instruments
100 amu Quadrupole
Saturn Ion Trap
Field deployment instrument
200 amu Quadrupole
Recent deployments
Bayboro Harbor
Lake Maggiore
Kennedy Space Center
Lake Yellowstone
Future Development

Schematics of underwater MS systems
Hulls: anodized Aluminum, depth 300 m; Power: 24 VDC;
Roughing Pump: 2 diaphragm pumps (KNF); Vacuum: Turbo pump (Varian)
Membrane Probe: PDMS (in house)
Analyzer Section
Quadrupole 100 amu
(Transpector 2, Inficon)
95 Watts, Length 125 cm,
Diameter 19 cm, Weight
in air 38 kg.
Analyzer Section
Iontrap (Saturn 2000, Varian)
150 Watts, Length 135 cm,
Diameter 19 cm in the
middle 32.5 cm,
Weight in air 68 kg.
Underwater Quadrupole
Underwater Ion trap

200 amu Linear Quadrupole MIMS System
Turbo pump
Quad
DSL converter
Embedded PC
Electronics
Roughing Pump
Membrane probe

Underwater Mass Spectrometry
Principle features of MS
Type
Linear quadrupole mass spectrometer
Mass range
200 amu
Inlet System
Membrane introduction system
Power consumption
105 Watts
Voltage of operation
24 V
Deployment time
10-14 days max.
Dimensions ∅ 19 cm (7.5”)
L 114 cm (45’’)
Weight
33 kg (72.7 Lb)
Depth
200 m max.
DSL tether range
1609 m (1 mile)

Modular Stepwise MS Approach
No configuration valid for all analytes
Less complex configuration first
Membrane introduction/quadrupole MS
Shallow water applications
Progressive versions
Solid-phase micro-extraction interface
Magnetic Sector MS for DIC, CO 2
Increased depth
Use common components

Membrane Introduction for
In-Situ Analysis
Simple Interface
PDMS Capillary
VOCs, Dissolved
Gases No Sample
Prep
In-line Sample
Heating
Membrane Probe Construction

Membrane Introduction
Sample Interface for High Pressure
Vacuum
Water in
Water out

Membrane Introduction
Sample Interface
Membrane
Assembly
Silicone
Membrane
Stainless Steel
Tube
Stainless
Steel Rod
Stainless
Steel Spring
Heaters
Thermocouple

Magnetic Piston Sample Pump
For Sampling at Depth

Target Analytes for
Underwater MIMS
Gases
CH 4 , N 2 , O 2 , CO 2 , Ar, etc.
(very low ppm, ~10 sec response)
Volatile Organic Compounds
Benzene, Toluene, Xylene, Dimethyl sulfide, etc.
(very low ppb, ~1-5 min response)
Semi-Volatile Compounds
Napthalene, PAHs, Pesticides, etc.
(low ppb, ~5-20 min response)

Deployments
Moored
Monitoring marinas and shipping
channels, tidal changes, river effluent
Guided surface vehicle
Mapping of voc’s and gases
Remotely Operated Vehicle
Chemical characterization of geothermal
plumes in Lake Yellowstone

Chemical Surveying using
Surface Vehicle
Deployment in Bayboro Harbor
ENG Concepts Guided Surface Vehicle

12:40:04
12:38:01
4.50E-11
4.00E-11
3.50E-11
3.00E-11
2.50E-11
2.00E-11
1.50E-11
1.00E-11
5.00E-12
0.00E+00
MS Data from Survey of Bayboro
Harbor
m/z 91
MASS( 47 ) MASS( 62 ) MASS( 78 ) MASS( 83 )
MASS( 85 ) MASS( 91 ) MASS( 92 )
m/z 78
m/z 92
m/z 62
11:13:55
11:15:58
11:18:01
11:20:09
11:22:11
11:24:14
11:26:17
11:28:19
11:30:22
11:32:24
11:34:27
11:36:30
11:38:32
11:40:35
11:42:43
11:44:46
11:46:48
11:48:51
11:50:54
11:52:57
11:54:59
11:57:02
11:59:04
12:01:07
12:03:10
12:05:12
12:07:15
12:09:17
12:11:20
12:13:29
12:15:32
12:17:34
12:19:37
12:21:39
12:23:42
12:25:45
12:27:47
12:29:50
12:31:53
12:33:55
12:35:58
Time

Mapping of Dimethyl Sulfide and
Toluene
Map variation in m/z 62 Intensity - Bayboro Harbor, Oct. 9, 2002
7 7
m/z 62
7
.
7 7
m/z 91
Map variation in m/z 91 Intensity - Bayboro Harbor, Oct. 9, 2002
7
.
Legend
m/z 62 - picoamperes
7 1.271 - 1.945
7 1.946 - 2.316
7 2.317 - 2.735
7 2.736 - 3.282
7 3.283 - 3.910
77
7
7
777 7
777 7 77 77
7
77 77
77 7
7777777777
7
77
777 7777 77
7 777
7 7
7
777777
7777 777
77
7777
777 7
777 7777
7
777
7
7 7
77
7 77777777
7
77777 7
77 7 7
77
7 777 7 7 77
7 7777 7
77
7
7
7 7
7 7
7 7 7
Legend
m/z 91 - picoamperes
7 9.670 - 13.000
7 13.001 - 15.200
7 15.201 - 16.700
7 16.701 - 18.900
7 18.901 - 22.000
77
7
7
777 7
777 7 77 77
7
77 77
77 7
7777777777
7
77
777 7777 77
7 777
7 7
7
777777
777 777
77
7777
777 7
777 7777
7
777
7
77
7 77777777
7
77777 7
77 7 7
77
7 777 7 7 77
7 7777 7
77
7
7
7 7
7 7
7 7 7
7 3.911 - 4.658
7 4.659 - 6.183
7 6.184 - 8.429
7
7
7
7
7 22.001 - 25.800
7 25.801 - 29.600
7 29.601 - 33.200
7
7
7
7
7 8.430 - 11.078
7 33.201 - 37.600
7 11.079 - 13.666
7 37.601 - 42.600
7
7
7
7
7 7 77
7
7 7
77 77 7
77
77 7
7
7
7
7
7
7
7 7 77
7
7 7
77 7
77
77
7
7
7
0 25 50 100 150 200
Meters
0 25 50 100 150 200
Meters

Chemical Surveying of
Lake Maggiore
Updated ENG Concepts
Guided Surface Vehicle

4429
4321
4213
4105
7.00E-09
6.00E-09
5.00E-09
4.00E-09
3.00E-09
2.00E-09
1.00E-09
0.00E+00
MS Data from Survey of Lake
Maggiore
O 2
m/z 32 m/z 44
CO 2
1
3997
109
217
325
433
541
649
757
865
973
1081
1189
1297
1405
1513
1621
1729
1837
1945
2053
2161
2269
2377
2485
2593
2701
2809
2917
3025
3133
3241
3349
3457
3565
3673
3781
3889
Scan number
Intensity

Mapping of Dissolved Gases
Map variation in m/z 32 intensity
Map variation in m/z 44 intensity

Joint Environmental Science Investigations
Conducted at the Kennedy Space Center
KENNEDY SPACE CENTER (KSC)
JOINT ENVIRONMENTAL SCIENCE INVESTIGATIONS (JESI)
TEST PLAN
AUGUST 2003
Principle Point of C ontact: A lte rnate Point of C ontact:
D e nis e M . C rim m ins J as on A . Yozura
Code 82201 Code 82201 Contractor
Naval Undersea Warfare Center Naval Undersea Warfare Center
401-832-9411 401-832-2395
crimminsdm@ npt.nuw c.navy.mil yozuraja@ npt.nuw c.navy.mil

UMS Deployed on the FMRI’s MARVIN Platform at
Kennedy Space Center

Mapping of O 2 during transect of the
Banana River

Deployment of UMS aboard a ROV
at Lake Yellowstone
110 VAC-24 VDC Power
Supply/DSL Hub
Mass
Spec
24 VDC Battery Pack

Tethered Deployment Scheme of UMS for
Lake Yellowstone
110 VAC – 24 VDC Power Supply /
DSL Converter
DSL Hub & 110 VAC
Power Switch
24 VDC Supply
Line to MS
200m Underwater Power &
Communication Tether
DSL Communication
Cable to MS
Underwater Mass Spectrometer
Laptop Computer
110 VAC
Power

Step One: Freeze the Mass Spec

Step Two: Deploy in a Blizzard

Lake Yellowstone transect
Bridge Bay to Mary Bay (m/z 44)

m/z 28, 32, 34, 40, 44 & 45 Intensities at
Otter Vent (3m), Lake Yellowstone
1.00E-07
1.00E-08
Mass Spec
entered vent
Mass Spec left
vent
m/z 32
Mass Spec reenters
vent
m/z 28
Intensity
1.00E-09
1.00E-10
m/z 44
m/z 32
m/z 40
m/z 44
MASS( 28 )
MASS( 32 )
MASS( 34 )
MASS( 40 )
MASS( 44 )
MASS( 45 )
1.00E-11
1.00E-12
m/z 34
m/z 45
0 100 200 300 400 500 600 700 800
Scan #

m/z 15, 32, 34, 44, 45 Intensities at
Vent (30 m) in Lake Yellowstone
1.00E-07
1.00E-08
m/z 44
m/z 28
Intensity
1.00E-09
1.00E-10
1.00E-11
m/z 32
m/z 40
m/z 34
m/z 15
MASS( 28 )
MASS( 32 )
MASS( 34 )
MASS( 40 )
MASS( 44 )
MASS( 45 )
MASS( 15 )
m/z 45
1.00E-12
0 100 200 300 400 500 600 700
Scan #

Even an Underwater Mass
Spectrometer needs a Break

Future Development Plans
Alternative Sampling Interfaces
Solid Phase Extraction (SPME)
In-line Acidification
DIC to CO 2
In-situ Magnetic Sector Instrument
Intelligent Ion, Inc.
Unattended Remote
Operation
Ocean observatory
Full Ocean Depths

Acknowledgements
Funding from U.S. Office of Naval Research (ONR) Grant No.
N00014-98-1-0154, N00014-03-1-0479
Gottfried Kibelka, Chad Lembke, Scott Samson, Charlie Jones, Joe
Kolesar, Eric Steimle (Center for Ocean Technology)
Bob Byrne, and Tom Peacock (USF College of Marine Science)
Richard Hildebrand, O. Manuel Uy (Johns Hopkins University,
Applied Physics Lab)
Denise Crimmins (NUWC)
Barbara Peterson (Dynamac Corp., KSC)
Val Klump, Rob Paddock, Jim Waples (University of Wisconsin,
Milwaukee)
Dave Lovalvo (Eastern Oceanics)