US008299424B2
(12) United States Patent
(10) Patent N0.:
Camilli
(54)
US 8,299,424 B2
(45) Date of Patent:
SYSTEMS AND METHODS FOR ANALYZING
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Oct. 30, 2012
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OTHER PUBLICATIONS
(75)
Inventor:
Richard Camilli’ Woods Hole’ MA (Us)
(73)
A _
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00 s 0 e ceanograp 1c
Harry Hemond and Richard Camilli, NEREUS: engineering concept
for an underwater mass spectrometer, 2002, trends in analytical
Chemistry, Vol‘ 21, NO‘ 8,1)‘ 526533,.
Institution, Woods Hole, MA (Us)
Harry Hemond and Richard Camilli, NEREUS/Kemonaut, a mobile
Subject to any disclaimer, the term of this
Direct, Trends in analytical chemistry, vol. 23, issue 4, pp. 307-3 13*
patent is extended or adjusted under 35
Camilli et al. “Underwater vacuum technology”, Vacuum Technol
ogy and coating, Dec. 2005, pp. 34-39.*
U'S'C' 154(1)) by 465 days‘
Hock et al. “A mass spectrometer inlet system for sampling gases
dissolved in liquid phases”, Archives of Biochemistry and Biophys
ics, vol. 101, Issue 1, Apr. 1963, pp. 160-170.*
autonomous underwater mass spectrometer, Apr. 2004, Science
(*)
(21)
Notice:
App1.No.: 11/796,874
International Search Report for PCT/U S2008/ 005288 mailed Aug. 7,
(22) Filed:
Apr. 30, 2007
(65)
2009
*
Prior Publication Data
Us 2009/0084976 A1
Apr' 2’ 2009
't d b
C1 e
'
y examlner
Primary Examiner i Michael Logie
(74) Attorney, Agent, or Firm * Ropes & Gray LLP
(51)
Int. Cl.
H01J 49/00
(52)
US. Cl. ..... .. 250/288; 250/281; 250/282; 73/5301;
73/6456
other things, systems capable of being deployed for long
(58)
Field of Classi?cation Search ................ .. 250/288,
250/298 281 282, 73 /6 4 56 53 01
Penods Oftlme “1 Oceamc, FHbSmYfaCe and atmosphenc en“
ronments. The systems typically include mass spectrometers
See a
to measure low molecular weight gases dissolved in the water
and volatile chemicals in air and Water, and can move through
the ocean, subsurface and atmospheric environment to take
samples over a large geographic area. Additionally, these
pp
(56)
(2006.01)
(57)
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References Cited
'
U S PATENT DOCUMENTS
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mass spectrometer devices are small and require little power
and thereby facilitate the development of sample collection
$219231; et 31
3’828’527 A *
8/1974 Briggs gt a1‘
5,313,061 A *
5,639,956 A *
5/1994 Drew et a1, ,,
6/1997 Christy ...... ..
96/5
devices that can be placed at a remote location and operated
96/4
for a substantial period of time from an on-board power
,, 250/2g1
. 73/1901
supply such as a battery or a fuel cell. Such small and light
weight mass spectrometer devices when combined with low
6,309,184 B1 : 10/2001 Mom]a et a1~
*
417/51
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"
2002/0079’441 A1 *
6/2002 Fries>etal.m...w
...... 250/281
6/2002
.... .. 250/281
Fries et al.
power AUVs (Autonomous Underwater Vehicles) and other
manned and un-manned vehicles, can take samples over sub
2002/0079442 A1 *
2005/0230614 A1 *
ABSTRACT
The systems and methods described herein include, among
stamial distances and for a Substantial Pen'od Of?me
10/2005 Glukhoy ..................... .. 250/287
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1
2
SYSTEMS AND METHODS FOR ANALYZING
UNDERWATER, SUBSURFACE AND
urban centers Where the speed and accuracy of detection can
save lives in the event of chemical spills or acts of bio
ATMOSPHERIC ENVIRONMENTS
terrorism. Similarly, in oil and natural gas applications, there
BACKGROUND
is a need for measuring volatile gases such as hydrocarbons
While controlling the seepage of Water vapor into the instru
mentation. Current systems typically utiliZe infra-red sensors
There is an increasing need for long term observation of the
earth-ocean system. In particular, there is a need to study,
that are prone to error from unWanted atmospheric Water
identify and quantify the chemical constituents present in the
more, current systems do not utiliZe more sensitive mass
vapor molecules entering the measurement system. Further
Water column including dissolved gases such as methane,
spectrometers because they require the continuous mainte
hydrogen sul?de, nitrogen, carbon dioxide and oxygen. A
nance of loW pressure conditions and strict control of sub
study of the chemical constituents enables scientists to track
changes in theses chemicals over time and thereby monitor
oceanic processes as Well as improve predictive modeling of
complex natural phenomena that vary over a longer time
scale. In general, such a study has a Wide range of scienti?c,
industrial, environmental and military uses including moni
stances entering the instrumentation.
Accordingly, there is a need for compact systems capable
of being operated With mass spectrometers to analyZe oce
anic, atmospheric and subsurface environments. Generally,
there is a need for a compact system to sample and detect
volatile substances and dissolved gases in both underWater as
Well as atmospheric environments both over and under the
surface of the earth.
toring shipping lanes, and monitoring and mitigating haZard
ous chemicals.
Cabled observatories located near the ocean bed alloW for
20
continuous in- situ sampling of the underWater environments
at desired sites. Since they are typically located in a particular
site and tethered to the ocean ?oor, they have several advan
The systems and methods described herein include, among
tages including having ability to capture signi?cant transient
other things, submersible systems capable of being deployed
phenomena and sudden changes in the ocean environment,
and since they are in-situ, eliminating the problems associ
ated With sample transportation and storage. HoWever, cur
rent technologies for studying the chemical constituents
using these cabled observatories for reliable long-term opera
SUMMARY OF THE INVENTION
25
for long periods of time near the ocean bed. The systems and
methods described herein also include, among other things,
systems capable of detecting substances in atmospheric and
tion underWater are limited. These cabled observatories are 30
subsurface environments.
In one aspect, the systems typically include mass spec
trometers to measure loW molecularWeight gases dissolved in
typically equipped With commercially available dissolved gas
the Water and can be moved through the ocean environment to
sensors, such as the Clark type oxygen electrode, that are
take samples over a large geographic area. Additionally, these
capable of measuring only single gas species and operate for
mass spectrometer devices are small and require little poWer
and thereby facilitate the development of sample collection
only a feW Weeks before degrading in performance. More
powerful instrumentation such as gas chromato graphs are not
35
suited for autonomous long-term underWater operation since
they need consumables and require regular maintenance. An
increasing trend is the use of mass spectrometers in cabled
observatories.
Mass spectrometers are Well suited for in-situ analysis of
dissolved gases and volatile chemicals in the Water column,
40
because they can quickly detect multiple dissolved chemicals
at loW concentrations, and can Work Without exhaust or con
sumable reagents. HoWever, current autonomous platforms
such as moorings, toW ?sh and autonomous underWater
capability. Additionally, they are unable to adequately resolve
housing and capable of maintaining a vacuum and connected
50
detecting one or more of the substances, and a permanent
magnet assembly may be disposed near the vacuum chamber
for generating a substantially homogeneous magnetic ?eld
55
reliable system for detecting hazardous gases in populated
Within a portion of the analyZer. In certain embodiments, the
systems are adapted to perform chemical analysis of sub
stances in an underWater environment at depths greater than
Accordingly, there is a need for a submersible system to
trometer devices that can facilitate, among other things,
mobile sensing devices that may move through the ocean
environment and take samples over a large geographic area.
In addition to analyZing underWater environments, there is
a need for accurate observation of atmospheric and subsur
face environments. In particular, there is a need for a fast and
to the inlet assembly for receiving the one or more substances.
An analyZer may be disposed Within the vacuum chamber for
perform long-term series sampling of dissolved gases in a
Water column in the ocean depths (e. g., at depths greater than
2500 m). There is also a need for a reduced siZe mass spec
The systems may comprise a housing and an inlet assembly,
connected to the housing and capable of alloWing one or more
substances from the underWater environment to diffuse into
the housing. A vacuum chamber may be disposed Within the
sea?oor use because they do not have the endurance or depth
“Creation and Deployment of the NEREUS Autonomous
UnderWater Chemical AnalyZer and Kemonaut, an Odyssey
Class Submarine” dated May 2003 and MIT Masters thesis
titled “The Development of Components for In-Situ Mass
Spectrometer” dated May 2000, the contents of each of Which
are incorporated herein by reference in their entirety.
Weight mass spectrometer devices When combined With loW
poWer AUVs (Autonomous UnderWater Vehicles), can take
samples over substantial distances and for a substantial period
of time.
In particular, the systems and methods disclosed herein
include systems for performing a chemical analysis of sub
stances in an underWater environment at a particular depth.
45
vehicles utiliZing mass spectrometers preclude long-term
loW mass chemicals such as hydrogen, helium and methane.
Such systems are described in the MIT PhD thesis titled
devices that can be placed at a remote location and operated
for a substantial period of time from an on-board poWer
supply such as a battery or a fuel cell. Such small and light
2500 meters.
The inlet assembly may be capable of Withstanding exter
60
nal pressures greater than about 500 atmospheres for an
extended period of time, While being subjected to internal
pressures of about 10'8 Torr Within the housing. The inlet
assembly may include an inlet membrane. The inlet mem
brane may be formed from hydrophobic materials and/or
65
materials having sloW permeability rate constants, high tem
perature coef?cients and high tensile strengths. In certain
embodiments, the inlet membrane may comprise a polymer.