Underwater mass spectrometers to monitor coastal waters, harbors ...
Underwater mass spectrometers to monitor coastal waters, harbors ...
Underwater mass spectrometers to monitor coastal waters, harbors ...
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Real-time Moni<strong>to</strong>ring of Aquatic Environments with<br />
an <strong>Underwater</strong> Mass Spectrometer<br />
Peter G. Wenner, F.H.W. van Amerom, S.K. Toler, J.E. Edkins,<br />
K. Koehn, R.J. Bell, M. Hall and R.T. Short<br />
University of South Florida Center for Ocean Technology
USF/COT <strong>Underwater</strong> Mass Spectrometry Program<br />
First generation instruments<br />
100 amu Quadrupole<br />
Saturn Ion Trap<br />
Field deployment instrument<br />
200 amu Quadrupole<br />
Recent deployments<br />
Bayboro Harbor<br />
Lake Maggiore<br />
Kennedy Space Center<br />
Lake Yellows<strong>to</strong>ne<br />
Future Development
Schematics of underwater MS systems<br />
Hulls: anodized Aluminum, depth 300 m; Power: 24 VDC;<br />
Roughing Pump: 2 diaphragm pumps (KNF); Vacuum: Turbo pump (Varian)<br />
Membrane Probe: PDMS (in house)<br />
Analyzer Section<br />
Quadrupole 100 amu<br />
(Transpec<strong>to</strong>r 2, Inficon)<br />
95 Watts, Length 125 cm,<br />
Diameter 19 cm, Weight<br />
in air 38 kg.<br />
Analyzer Section<br />
Iontrap (Saturn 2000, Varian)<br />
150 Watts, Length 135 cm,<br />
Diameter 19 cm in the<br />
middle 32.5 cm,<br />
Weight in air 68 kg.<br />
<strong>Underwater</strong> Quadrupole<br />
<strong>Underwater</strong> Ion trap
200 amu Linear Quadrupole MIMS System<br />
Turbo pump<br />
Quad<br />
DSL converter<br />
Embedded PC<br />
Electronics<br />
Roughing Pump<br />
Membrane probe
<strong>Underwater</strong> Mass Spectrometry<br />
Principle features of MS<br />
Type<br />
Linear quadrupole <strong>mass</strong> spectrometer<br />
Mass range<br />
200 amu<br />
Inlet System<br />
Membrane introduction system<br />
Power consumption<br />
105 Watts<br />
Voltage of operation<br />
24 V<br />
Deployment time<br />
10-14 days max.<br />
Dimensions ∅ 19 cm (7.5”)<br />
L 114 cm (45’’)<br />
Weight<br />
33 kg (72.7 Lb)<br />
Depth<br />
200 m max.<br />
DSL tether range<br />
1609 m (1 mile)
Modular Stepwise MS Approach<br />
No configuration valid for all analytes<br />
Less complex configuration first<br />
Membrane introduction/quadrupole MS<br />
Shallow water applications<br />
Progressive versions<br />
Solid-phase micro-extraction interface<br />
Magnetic Sec<strong>to</strong>r MS for DIC, CO 2<br />
Increased depth<br />
Use common components
Membrane Introduction for<br />
In-Situ Analysis<br />
Simple Interface<br />
PDMS Capillary<br />
VOCs, Dissolved<br />
Gases No Sample<br />
Prep<br />
In-line Sample<br />
Heating<br />
Membrane Probe Construction
Membrane Introduction<br />
Sample Interface for High Pressure<br />
Vacuum<br />
Water in<br />
Water out
Membrane Introduction<br />
Sample Interface<br />
Membrane<br />
Assembly<br />
Silicone<br />
Membrane<br />
Stainless Steel<br />
Tube<br />
Stainless<br />
Steel Rod<br />
Stainless<br />
Steel Spring<br />
Heaters<br />
Thermocouple
Magnetic Pis<strong>to</strong>n Sample Pump<br />
For Sampling at Depth
Target Analytes for<br />
<strong>Underwater</strong> MIMS<br />
Gases<br />
CH 4 , N 2 , O 2 , CO 2 , Ar, etc.<br />
(very low ppm, ~10 sec response)<br />
Volatile Organic Compounds<br />
Benzene, Toluene, Xylene, Dimethyl sulfide, etc.<br />
(very low ppb, ~1-5 min response)<br />
Semi-Volatile Compounds<br />
Napthalene, PAHs, Pesticides, etc.<br />
(low ppb, ~5-20 min response)
Deployments<br />
Moored<br />
Moni<strong>to</strong>ring marinas and shipping<br />
channels, tidal changes, river effluent<br />
Guided surface vehicle<br />
Mapping of voc’s and gases<br />
Remotely Operated Vehicle<br />
Chemical characterization of geothermal<br />
plumes in Lake Yellows<strong>to</strong>ne
Chemical Surveying using<br />
Surface Vehicle<br />
Deployment in Bayboro Harbor<br />
ENG Concepts Guided Surface Vehicle
12:40:04<br />
12:38:01<br />
4.50E-11<br />
4.00E-11<br />
3.50E-11<br />
3.00E-11<br />
2.50E-11<br />
2.00E-11<br />
1.50E-11<br />
1.00E-11<br />
5.00E-12<br />
0.00E+00<br />
MS Data from Survey of Bayboro<br />
Harbor<br />
m/z 91<br />
MASS( 47 ) MASS( 62 ) MASS( 78 ) MASS( 83 )<br />
MASS( 85 ) MASS( 91 ) MASS( 92 )<br />
m/z 78<br />
m/z 92<br />
m/z 62<br />
11:13:55<br />
11:15:58<br />
11:18:01<br />
11:20:09<br />
11:22:11<br />
11:24:14<br />
11:26:17<br />
11:28:19<br />
11:30:22<br />
11:32:24<br />
11:34:27<br />
11:36:30<br />
11:38:32<br />
11:40:35<br />
11:42:43<br />
11:44:46<br />
11:46:48<br />
11:48:51<br />
11:50:54<br />
11:52:57<br />
11:54:59<br />
11:57:02<br />
11:59:04<br />
12:01:07<br />
12:03:10<br />
12:05:12<br />
12:07:15<br />
12:09:17<br />
12:11:20<br />
12:13:29<br />
12:15:32<br />
12:17:34<br />
12:19:37<br />
12:21:39<br />
12:23:42<br />
12:25:45<br />
12:27:47<br />
12:29:50<br />
12:31:53<br />
12:33:55<br />
12:35:58<br />
Time
Mapping of Dimethyl Sulfide and<br />
Toluene<br />
Map variation in m/z 62 Intensity - Bayboro Harbor, Oct. 9, 2002<br />
7 7<br />
m/z 62<br />
7<br />
.<br />
7 7<br />
m/z 91<br />
Map variation in m/z 91 Intensity - Bayboro Harbor, Oct. 9, 2002<br />
7<br />
.<br />
Legend<br />
m/z 62 - picoamperes<br />
7 1.271 - 1.945<br />
7 1.946 - 2.316<br />
7 2.317 - 2.735<br />
7 2.736 - 3.282<br />
7 3.283 - 3.910<br />
77<br />
7<br />
7<br />
777 7<br />
777 7 77 77<br />
7<br />
77 77<br />
77 7<br />
7777777777<br />
7<br />
77<br />
777 7777 77<br />
7 777<br />
7 7<br />
7<br />
777777<br />
7777 777<br />
77<br />
7777<br />
777 7<br />
777 7777<br />
7<br />
777<br />
7<br />
7 7<br />
77<br />
7 77777777<br />
7<br />
77777 7<br />
77 7 7<br />
77<br />
7 777 7 7 77<br />
7 7777 7<br />
77<br />
7<br />
7<br />
7 7<br />
7 7<br />
7 7 7<br />
Legend<br />
m/z 91 - picoamperes<br />
7 9.670 - 13.000<br />
7 13.001 - 15.200<br />
7 15.201 - 16.700<br />
7 16.701 - 18.900<br />
7 18.901 - 22.000<br />
77<br />
7<br />
7<br />
777 7<br />
777 7 77 77<br />
7<br />
77 77<br />
77 7<br />
7777777777<br />
7<br />
77<br />
777 7777 77<br />
7 777<br />
7 7<br />
7<br />
777777<br />
777 777<br />
77<br />
7777<br />
777 7<br />
777 7777<br />
7<br />
777<br />
7<br />
77<br />
7 77777777<br />
7<br />
77777 7<br />
77 7 7<br />
77<br />
7 777 7 7 77<br />
7 7777 7<br />
77<br />
7<br />
7<br />
7 7<br />
7 7<br />
7 7 7<br />
7 3.911 - 4.658<br />
7 4.659 - 6.183<br />
7 6.184 - 8.429<br />
7<br />
7<br />
7<br />
7<br />
7 22.001 - 25.800<br />
7 25.801 - 29.600<br />
7 29.601 - 33.200<br />
7<br />
7<br />
7<br />
7<br />
7 8.430 - 11.078<br />
7 33.201 - 37.600<br />
7 11.079 - 13.666<br />
7 37.601 - 42.600<br />
7<br />
7<br />
7<br />
7<br />
7 7 77<br />
7<br />
7 7<br />
77 77 7<br />
77<br />
77 7<br />
7<br />
7<br />
7<br />
7<br />
7<br />
7<br />
7 7 77<br />
7<br />
7 7<br />
77 7<br />
77<br />
77<br />
7<br />
7<br />
7<br />
0 25 50 100 150 200<br />
Meters<br />
0 25 50 100 150 200<br />
Meters
Chemical Surveying of<br />
Lake Maggiore<br />
Updated ENG Concepts<br />
Guided Surface Vehicle
4429<br />
4321<br />
4213<br />
4105<br />
7.00E-09<br />
6.00E-09<br />
5.00E-09<br />
4.00E-09<br />
3.00E-09<br />
2.00E-09<br />
1.00E-09<br />
0.00E+00<br />
MS Data from Survey of Lake<br />
Maggiore<br />
O 2<br />
m/z 32 m/z 44<br />
CO 2<br />
1<br />
3997<br />
109<br />
217<br />
325<br />
433<br />
541<br />
649<br />
757<br />
865<br />
973<br />
1081<br />
1189<br />
1297<br />
1405<br />
1513<br />
1621<br />
1729<br />
1837<br />
1945<br />
2053<br />
2161<br />
2269<br />
2377<br />
2485<br />
2593<br />
2701<br />
2809<br />
2917<br />
3025<br />
3133<br />
3241<br />
3349<br />
3457<br />
3565<br />
3673<br />
3781<br />
3889<br />
Scan number<br />
Intensity
Mapping of Dissolved Gases<br />
Map variation in m/z 32 intensity<br />
Map variation in m/z 44 intensity
Joint Environmental Science Investigations<br />
Conducted at the Kennedy Space Center<br />
KENNEDY SPACE CENTER (KSC)<br />
JOINT ENVIRONMENTAL SCIENCE INVESTIGATIONS (JESI)<br />
TEST PLAN<br />
AUGUST 2003<br />
Principle Point of C ontact: A lte rnate Point of C ontact:<br />
D e nis e M . C rim m ins J as on A . Yozura<br />
Code 82201 Code 82201 Contrac<strong>to</strong>r<br />
Naval Undersea Warfare Center Naval Undersea Warfare Center<br />
401-832-9411 401-832-2395<br />
crimminsdm@ npt.nuw c.navy.mil yozuraja@ npt.nuw c.navy.mil
UMS Deployed on the FMRI’s MARVIN Platform at<br />
Kennedy Space Center
Mapping of O 2 during transect of the<br />
Banana River
Deployment of UMS aboard a ROV<br />
at Lake Yellows<strong>to</strong>ne<br />
110 VAC-24 VDC Power<br />
Supply/DSL Hub<br />
Mass<br />
Spec<br />
24 VDC Battery Pack
Tethered Deployment Scheme of UMS for<br />
Lake Yellows<strong>to</strong>ne<br />
110 VAC – 24 VDC Power Supply /<br />
DSL Converter<br />
DSL Hub & 110 VAC<br />
Power Switch<br />
24 VDC Supply<br />
Line <strong>to</strong> MS<br />
200m <strong>Underwater</strong> Power &<br />
Communication Tether<br />
DSL Communication<br />
Cable <strong>to</strong> MS<br />
<strong>Underwater</strong> Mass Spectrometer<br />
Lap<strong>to</strong>p Computer<br />
110 VAC<br />
Power
Step One: Freeze the Mass Spec
Step Two: Deploy in a Blizzard
Lake Yellows<strong>to</strong>ne transect<br />
Bridge Bay <strong>to</strong> Mary Bay (m/z 44)
m/z 28, 32, 34, 40, 44 & 45 Intensities at<br />
Otter Vent (3m), Lake Yellows<strong>to</strong>ne<br />
1.00E-07<br />
1.00E-08<br />
Mass Spec<br />
entered vent<br />
Mass Spec left<br />
vent<br />
m/z 32<br />
Mass Spec reenters<br />
vent<br />
m/z 28<br />
Intensity<br />
1.00E-09<br />
1.00E-10<br />
m/z 44<br />
m/z 32<br />
m/z 40<br />
m/z 44<br />
MASS( 28 )<br />
MASS( 32 )<br />
MASS( 34 )<br />
MASS( 40 )<br />
MASS( 44 )<br />
MASS( 45 )<br />
1.00E-11<br />
1.00E-12<br />
m/z 34<br />
m/z 45<br />
0 100 200 300 400 500 600 700 800<br />
Scan #
m/z 15, 32, 34, 44, 45 Intensities at<br />
Vent (30 m) in Lake Yellows<strong>to</strong>ne<br />
1.00E-07<br />
1.00E-08<br />
m/z 44<br />
m/z 28<br />
Intensity<br />
1.00E-09<br />
1.00E-10<br />
1.00E-11<br />
m/z 32<br />
m/z 40<br />
m/z 34<br />
m/z 15<br />
MASS( 28 )<br />
MASS( 32 )<br />
MASS( 34 )<br />
MASS( 40 )<br />
MASS( 44 )<br />
MASS( 45 )<br />
MASS( 15 )<br />
m/z 45<br />
1.00E-12<br />
0 100 200 300 400 500 600 700<br />
Scan #
Even an <strong>Underwater</strong> Mass<br />
Spectrometer needs a Break
Future Development Plans<br />
Alternative Sampling Interfaces<br />
Solid Phase Extraction (SPME)<br />
In-line Acidification<br />
DIC <strong>to</strong> CO 2<br />
In-situ Magnetic Sec<strong>to</strong>r Instrument<br />
Intelligent Ion, Inc.<br />
Unattended Remote<br />
Operation<br />
Ocean observa<strong>to</strong>ry<br />
Full Ocean Depths
Acknowledgements<br />
Funding from U.S. Office of Naval Research (ONR) Grant No.<br />
N00014-98-1-0154, N00014-03-1-0479<br />
Gottfried Kibelka, Chad Lembke, Scott Samson, Charlie Jones, Joe<br />
Kolesar, Eric Steimle (Center for Ocean Technology)<br />
Bob Byrne, and Tom Peacock (USF College of Marine Science)<br />
Richard Hildebrand, O. Manuel Uy (Johns Hopkins University,<br />
Applied Physics Lab)<br />
Denise Crimmins (NUWC)<br />
Barbara Peterson (Dynamac Corp., KSC)<br />
Val Klump, Rob Paddock, Jim Waples (University of Wisconsin,<br />
Milwaukee)<br />
Dave Lovalvo (Eastern Oceanics)