Abstract:
A gas-equilibrated, volatile-in-water detector comprises a gas-sensing chamber having an orifice closed by a hydrophobic, vapour-porous membrane, typically PTFE, sealed to the periphery of the orifice. Membrane is also sealed to an external wall of a surrounding enclosure and forms an entry point to a second gaseous enclosure external of the gas-sensing chamber. A PID or similar sensor generates a measurable current or voltage in response to the partial pressure of the analyte within the gas-sensing chamber without the sensor significantly altering such equilibrium partial pressure.

Description:
FIELD OF THE INVENTION 
       [0001]    This invention relates to detection of gaseous and volatile analytes dissolved in water and other aqueous fluids using a detector within which such materials are sensed in the gaseous phase. Analytes of particular interest are volatile organic compounds (VOCs) particularly as found in water and aqueous solutions in concentrations varying from less than a part per billion (ppb, 10 −9 ) to parts per thousand (ppt, 10 −3 ) by mass. 
       BACKGROUND OF THE INVENTION 
       [0002]    There is a need to detect and measure the presence of organic contaminants in natural and artificially contained sources of water and other aqueous fluids. VOCs include irritants, oestrogens, carcinogens and other chemicals harmful to humans, animals and plant life. Rigorous standards are laid down for potable water supplies which must be carefully monitored. Similarly, open water such as rivers, lakes and the oceans must be monitored for contamination or pollution to prevent damage to plants, animals or adjoining land. 
         [0003]    Volatile and gaseous compounds dissolved in water are also of interest as analytes due to other deleterious effects, for example in accelerating corrosion of metal pipes and vessels, or simply as indicators of water process quality within certain environments, for example wash water used in an industrial closed loop process or in the detection of alcohols due to fermentation in food stuffs and in brewing. 
         [0004]    It is frequently of interest to search for the presence of gaseous species within large expanses of water, and to trace their source and extent in near real time, as for example may arise from spillage of petrochemicals into sea water arising due to a natural event, an accident or clandestine activity. Such bodies of water are also subject to currents and drift. Current methods of analysis for trace quantities of VOCs and other dissolved gaseous species, such as chromatography or spectroscopy, are too slow and expensive to provide a dynamic map of volatile concentrations within water. Instead, it is preferable to submerge sensors for the target analytes within the body of water to provide a fast and quantitative measurement of their concentration. Such sensors may not provide the most accurate measure of target analytes, indeed, they may often be of most service in screening for unusual concentrations of a suite of different analytes in water samples, which are then selectively forwarded for more expensive and time consuming detailed analysis. 
         [0005]    A class of such detectors contain a membrane, typically hydrophobic, providing a barrier between the aqueous sensed environment and a detector enclosure, through which the analyte is able to diffuse. 
         [0006]    In one subclass of such detector, the detector enclosure contains an aqueous liquid. A well known example of this type of sensor is the ‘Clarke electrode’, in which dissolved oxygen in water diffuses from the test environment through a sensor membrane into an electrolyte, contained within a sensor cavity which includes the membrane as one containment wall member. The dissolved oxygen is consumed at an electrode proximal to the membrane. Patent DE20300514 U1, Achim Rappl, provides another example of this type of detector, again for detecting dissolved oxygen. 
         [0007]    In another subclass of such detectors, the detector membrane, which is in contact with the aqueous fluid on one side, forms the wall of a gaseous enclosure on the other, through which the analyte is able to diffuse. Hereinafter for convenience we shall refer to this type of detector as a gas partitioned volatile detector. 
         [0008]    U.S. Pat. No. 5,979,219, S Sellmer-Wilsberg et al. 
         [0009]    describes such a detector in which the membrane admits volatiles, which are then entrained within a carrier gas to a nearby gas sensor which is able to respond to a volatile such as ethanol. The carrier gas is needful to ensure that analyte entering the detector can be removed within a reasonable time frame. The need for carrier gas does however constrain the application of the device to circumstances in which a carrier gas flow can be supported. The carrier gas also acts as an analyte diluent, whereupon the sensitivity of a device provided by this invention is limited and its accuracy circumscribed by the extent of gas flow through the membrane. 
         [0010]    U.S. Pat. No. 5,979,219 describes another gas partitioned volatile detector in which the membrane admits volatiles such as ethanol into the sensing gaseous enclosure which is then sensed by a proximal semiconducting gas sensor. The invention relies on a pressure relief system being continuously open in order to ‘exhaust’ gases, not least target volatiles, into the atmosphere [Col 2 lines 11-32, Col 3, lines 26-35] rendering a carrier gas to flush the sensor enclosure unnecessary [Col 2 line 31]. A problem to be expected with a detector made according to US &#39;219 is that the rate of analyte escape from the detector gaseous chamber will be very slow and highly variable, according to factors which enable more or less rapid escape of gases from the pressure relief outlet to atmosphere at some considerable distance. The design may be sufficiently compact to enable detector response and cleardown in the time frame of half a day, as may be useful in brewing, but not within a minute or two, as may be required, for example, in sensing volatiles in a sensor train behind a boat or in a water process stream. 
         [0011]    U.S. Pat. No. 7,385,191 B1, assigned to Pacific Environmental Technologies, LLC, provides another illustration of a gas partitioned volatile detector in which a much more rapid response time is assured by the continuous vacuum purge required for the mass spectrometer sensing gases permeating the gas-permeable membrane. It is however, liable to be limited by the burden of cost and care that is need to maintain a vacuum system, not to mention practicalities of its being used in all weathers by persons who may have limited training in the use of vacuum systems. 
         [0012]    In the absence of an air purge or a gas release means or a vacuum system, a further means of analyte removal from a gas partitioned volatile detector may be provided by the gas sensor or gas sensing element itself consuming the analyte, as is illustrated in PCT/AU94/00714 (EP 0734516 A1), Commonwealth Scientific and Industrial Research Organisation, which describes an amperommetric oxygen sensor behind a diffusive membrane. 
         [0013]    Analyte detection may be contemplated by way of infrared sensors such as disclosed in U.S. Pat. No. 8,383,046 
         [0014]    Most prior art to date does not appear to include a gas partitioned volatile detector in which neither does the gas sensing element consume the analyte, nor does the detector use some means of gas evacuation to remove the analyte. One exception to this is U.S. Pat. No. 8,383,046 which utilises an IR detector typically having a volume of 400 mm 3 . This technology is dependent on having a relatively large volume sample in order to register the presence of the analyte. The downside of this is that the time taken to fill the chamber (by equilibration of analyte across a sensor membrane) to an appreciable level for a reading to be taken makes for a sensor whose response time is unacceptably high. 
         [0015]    The present invention recognises this and all previously described problems and attempts to mitigate them by way of a novel detector arrangement. Hereinafter for convenience we will refer to this type of detector as a gas-equilibrated, volatile-in-liquid detector. 
         [0016]    This detector provides a significant advantage over other gas-partitioned volatile detectors, in prospectively delivering a partial pressure of gas in the gaseous enclosure p in equilibrium with the concentration of gas in the liquid phase, c. When this condition is achieved, Henry&#39;s Law is obeyed. Specifically, p=k H ×c, where k H  is Henry&#39;s constant. Temperature dependent constants k H  are known for a plethora of important volatiles and thus, prospectively, the response of a gas sensing element can be directly related to the concentration of the gas in the liquid phase. Thus, it requires only the gas sensing element in the gas-equilibrated, volatile-in-liquid detector to be reliable in sensing a target analyte for the concentration of a volatile in an adjoining liquid phase to be known. The detector can provide a measurement of a volatile in a liquid which does not vary directly with the rate of supply of analyte to the sensor, as determined either: by the rate of consumption or dispersion of analyte by components within the detector; or by the permeability or porosity of any intervening membrane. 
         [0017]    A possible reason why the prior art may not have been directed towards gas-equilibrated, volatile-in-liquid detectors is that in order to achieve gas/liquid equilibrium, particularly for volatile analytes for which k H  is large and for which accordingly the volatile is only scarcely soluble in water, the volatile must be abstracted in substantial quantity from the sampled aqueous phase, and that that this volumetric demand for analyte on the sample side increases in proportion to the volume of the gaseous enclosure containing the gas sensing element. The gaseous enclosure within a gas-equilibrated, volatile-in-liquid detector is therefore required to be smaller than is demanded commonly of atmospheric gas sensing devices monitoring. Unlike other detectors engaging a water-gas partition, such as those of U.S. Pat. No. 5,979,219, U.S. Pat. No. 7,385,191 B1, DE20300514 U1 and PCT/AU94/00714 referred to above, the effectiveness of this type of detector requires the elimination of all means of removal of gas from the gaseous enclosure within the sensor except from the membrane itself. Achieving this condition is not trivial. 
         [0018]    Another problem we have encountered in the discovery of the present invention is that gas sensors and gas sensing sub-assemblies suitable for the measurement of analyte in equilibrium with an adjoining liquid phase commonly include a gaseous enclosure characterised by its being contiguous, sometimes unavoidably, with tortuous and convoluted gaseous spaces between sub-assembled components and with capillary leak sites, all of which provide an appreciable sink for analyte when compared to the slow rate of supply and removal of analyte though the partition separating the gas enclosure from the liquid containing the analyte. 
         [0019]    A further difficulty arises from the need to obtain a sufficient flux through the membrane separating an aqueous environment from a gaseous enclosure to ensure reasonably fast equilibration of the analyte within the gaseous enclosure. To obtain this, it is commonly preferable to engage a porous hydrophobic membrane as a partition between the liquid and the detector&#39;s gaseous enclosure. Placement and sealing of the membrane is problematic. Placement and seal at some separation from the gas sensor or sensing sub-assembly within the detector requires an intervening membrane support, to ensure the membrane does not rupture under a pressure presented by the liquid abutting its external face, as taught for example by U.S. Pat. No. 5,979,219. Remoteness of the membrane from the gas sensing element in an equilibrated detector adds significantly to the time required for equilibration of gas within an equilibrated detector. If the gaseous enclosure members are used to support and seal the membrane, without the use of an o-ring, and contrary to the normal practice in the art as to how such liquid/gas seals should be assured, then any membrane rupture or leakage will lead to ingress of liquid into the gaseous enclosure, prospectively proceeding to corrode electrically connected gaseous sensing components and causing the sensor to be worthless. 
       SUMMARY OF THE INVENTION 
       [0020]    We have invented a method of detecting and measuring organic materials in water, particularly at trace concentrations, which can provide real time measurements in a field environment, with little additional procedure than is required in the use of a typical gas detectors, and which enables easily calculated determination of the concentration of such organic materials in water, when their identity is known. 
         [0021]    According to aspect we provide a system for detecting or measuring gaseous or volatile analytes in an aqueous medium comprising as set forth in claim  1  of the appended claims. 
         [0022]    According to a further aspect we provide a sensor head for use in a detector of volatiles in aqueous media as set forth in claim  15  of the appended claims. 
         [0023]    Thus, we provide a detector of volatiles in water and aqueous fluids, which contains as one member a vapour-porous or vapour-permeable membrane forming a wall of a gaseous enclosure in which concentration of gas in the enclosure is substantively achieved by means of analyte flux through the membrane. 
         [0024]    The membrane may also be sealed to an external wall of the gas-sensing chamber or of a surrounding enclosure, which may form part of a separable gas sensing sub-assembly or easily removable sensor. This outer seal may be a peelable adhesive. Conveniently, the two seals are concentric. 
         [0025]    In this configuration, the vapour-porous or vapour-permeable membrane forms an entry point to a second gaseous enclosure external of the gas-sensing chamber. This can reduce the effect of leaks between sub-components of the sensor assembly, by enabling gas equilibration in the space between the gas sensor and walls containing it. 
         [0026]    It is preferable for the membrane sealing the gas sensing sub-assembly or gas sensor to extend beyond its point of sealing to the sensor to effect a further seal to outer detector components, such that, upon removal of the membrane, the gas sensor or sensor sub-assembly may be removed from the detector. To facilitate this, it is convenient for the gas sensor or gas sensing sub-assembly to receive gas from an orifice in a planar supporting surface, which is contrived to be in the plane of the termination of detector wall members to which the outer membrane seal is made. 
         [0027]    It is self-evident that, as far as possible, the membrane must exclude liquid water from the gas-sensing chamber. Conveniently, the membrane is hydrophobic. A suitable material is porous polytetrafluoroethylene (PTFE) or polyvinylidene difluoride (PVDF), either stand alone or as a coating on a porous substrate such as polypropylene. Typically, the overall thickness is some 100-500 m −6  and the pore size is approximately 0.5 m −6 . 
         [0028]    The seal to the outer membrane member may be effected by means of an adhesive layer on a hydrophobic surface such as PTFE. 
         [0029]    The membrane may contain an annulus of adhesive to effect sealing of the gas sensor or gas sensing subcomponent. 
         [0030]    Ideally, the seal to the periphery of the chamber orifice is a vapour-impermeable barrier throughout the thickness of the membrane. This is normally a weld, particularly ultrasonic, between the membrane material and the gas sensor or gas sensing sub-assembly but can also be an impermeable adhesive penetrating the membrane. 
         [0031]    The invention in a further aspect provides for membrane material between the outer membrane to detector wall seal and the inner gas membrane to gaseous sensor seal or membrane to gaseous sensing sub-assembly seal to be vapour-permeable or vapour-porous. 
         [0032]    It is preferable for all porous surfaces to comprise porous PTFE. 
         [0033]    Without limitation, it is believed that the vapour detector measures the partial pressure of the organic materials in the vapour phase. Particularly at low concentrations, this measurement is a function of the concentration of the organic material in the liquid water. 
         [0034]    Advantageously, the gas-sensing chamber is so configured as to minimise dead volume therein. Conveniently, the internal volume of the gas-sensing chamber is no greater than 100 mm 3 . 
         [0035]    Advantageously, the electrodes or other sensing system components within a sensor or sensing sub-assembly according to the present invention are stacked, with only a modest spacing between the sensing components such that the entire thickness of the sensing enclosure is no greater than a few millimetres. Thereby, the water from which organic volatiles pass through the membrane is in very close proximity to the entirety of the gas sensing enclosure, typically within 2 mm. The sensor may include a plurality of electrode contacts which, in an assembled position, lie in a common plane in the gas-sensing chamber and as close as possible to the overlying membrane. 
         [0036]    A particularly beneficial stacking arrangement for the electrodes is described and claimed in our patent GB 2449664 B, filed 30 Jun. 2007 (equivalent to U.S. Pat. No. 7,821,270 B2 issued 26 Oct. 2010 and others elsewhere). The electrode stack of this patent is well-suited to use with a miniature photoionisation detector. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0037]      FIG. 1  shows a schematic representation of a gas-equilibrated, volatile-in-water detector according to the invention. 
           [0038]      FIG. 2  is an elevation of the membrane assembly of  FIG. 1  prior to its deployment. 
           [0039]      FIG. 3  shows the membrane assembly of  FIG. 2  from a different perspective. 
           [0040]      FIG. 4  shows a schematic representation of a gas-equilibrated, volatile-in-water probe according to the invention wherein a gas sensor body contains a removable and replaceable gas receiving and sensing member. 
           [0041]      FIG. 5  shows a gas sensing replaceable sub-assembly prior to assembly in the probe shown schematically in  FIG. 4 . 
       
    
    
     DESCRIPTION OF EMBODIMENTS 
       [0042]    The invention will now be described in more detail by reference to the drawings provided. 
         [0043]      FIG. 1  shows a schematic representation of a gas-equilibrated, volatile-in-water detector provided by the invention, in which a gas sensor  1  is contained within a gas sensor cradle  2 . The gas sensor is preferably of cylindrical shape, and typically of 20 mm diameter and 16.6 mm height, excluding contact pins  3 , as provided as a received industrial standard by gas sensor manufacturers such as Alphasense Ltd, Dynament Ltd and City Technology Ltd. The gas sensor preferably is disposed to sit upon, and make electrical connection via  3  to, a small printed circuit board (PCB),  4 , itself electrically connected to a cable  5 , through which power is delivered to the gas sensor and signals are communicated to and from the sensor to some external means of control such as a computer, via, by way of example, a universal serial port. The cradle  2  and PCB  4  are positioned so that the face,  1   a,  of the gas sensor containing a gas sensing orifice  1   b,  is approximately co-planar with the cradle wall flat surfaces  2   a.  Gas porous PTFE membrane  6 , some 280-300 m −6  thick, is attached by means of a thin adhesive layer  7  to the sensor face  1   a.  A further portion  6   b  of the membrane is attached by means of a thin layer of adhesive  8  to the cradle wall flats  2   a,  thereby forming an entry point to a second gaseous enclosure external of the gas sensor  1 . The adhesive on the membrane does not extend beyond its point of contact to the gas sensor face  1   a  at the periphery of the gas sensing orifice  1   c.  Over at least its area of coverage of the gas orifice, the membrane portion  6   c  is on the contrary, substantially free of adhesives which could prevent gas flow into or out of the gas orifice. The invention also provides in one aspect an additional membrane component  6   d,  which extends beyond cradle wall segments  2   a,  enabling the membrane to be peeled off after field use, rather than being stored, possibly wet and contaminated, attached to other detector members. 
         [0044]      FIG. 2  shows the membrane assembly of  FIG. 1  prior to its deployment. Additional to the components already described, the membrane includes a waxed paper or other removable member  9  to protect adhesive portions of the membrane before use.  FIG. 3  shows the membrane assembly of  FIG. 2  from a different perspective, with the adhesive-protective element removed. 
         [0045]      FIG. 4  shows a schematic representation of a gas-equilibrated, volatile-in-water probe provided by the invention wherein a gas sensor body  10  contains a removable and replaceable gas receiving and sensing member  11 . An example of such a sensor is the 16.6 mm×20 mm diameter miniature photoionisation detector (PID) manufactured by Ion Science Limited and containing an electrode pellet as described and claimed in our GB 2449664 B. 
         [0046]    Sensor body  10  is seated on PCB  4 , with which it makes electrical contact by means of pins  3 . PCB  4  is also in electrical contact with cable  5 , as described in reference to corresponding components  3 ,  4  and  5  in  FIG. 1 . 
         [0047]    Gas sensing member  11  is approximately pellet shaped, and includes an orifice for receiving gas,  11   a,  on its outwardly facing major surface,  11   b,  opposing its other major surface proximal to the sensor body cavity (gas sensing chamber)  10   b  containing the gas sensing member  11 . Surface  11   b  of the gas sensing member  11  is approximately co-planar with sensor body surface  10   a,  and also approximately co-planar with cradle wall flats  2   a.    
         [0048]    Gas sensing member  11  is attached at annulus  11   c  to gas-porous or gas-permeable membrane  6  by means of an adhesive or ultrasonic welding of membrane portion  6   a  to the gas sensing member flat surface  11   b  close to the periphery of gas orifice  11   a.  It is preferable for the membrane portion  6   a  joined to gas sensing member portion  11   c  not to be porous or permeable to gas, either by virtue of an impermeable adhesive being applied to and impregnating the membrane, or by the membrane  6  and gas sensing member face  11   b  being welded at the point of fusion so as to form a seal that is neither porous nor appreciably permeable. 
         [0049]    The membrane  6  is also attached to cradle wall flats  2   a  by means of adhesive  13  at annulus  6   b,  thereby forming an entry point to a second gaseous enclosure  12  external of the gas-sensing chamber. The membrane is substantially porous or vapour-permeable over that portion overlaying gas orifice  11   a  and bounded by the impervious seal between annulus  6   a  and portion  11   c.  The membrane portion between annular seals  6   a  and  6   b  may or may not be porous or permeable according to the benefit conferred by enabling gaseous analyte gas irrigation at potential leak paths between probe members  10  and  11 . The membrane  6  further may include a tab  6   d  for convenient removal of the membrane  6  after use. 
         [0050]      FIG. 5  shows a replaceable gas sensing sub-assembly comprising components  11  and  6  prior to their assembly in the probe shown schematically in  FIG. 4 . This replaceable component includes a removable protective cover  14  to protect the adhesive portion of the membrane  6   b.    
         [0051]    The invention will now be described by reference to how it is operated in order to measure volatiles present in a watery liquid. 
         [0052]    In the case of a gas sensor containing an integral means of gas admittance, such as is described in  FIG. 1 , it is preferable for the sensor  1  to be removed from the cradle  2  over times of significant storage. The sensor is manually fitted in the cradle ensuring pins from the sensor  3  fit snugly into PCB platform  4 . The covering  9  is removed from a disposable membrane assembly such as shown in  FIG. 2 , and placed over the cradle wall flats  2   a  and sensor face  1   a  to make a seal. To ensure correct alignment of the membrane to the sensor face, such that a porous and permeable part of the membrane  6   c  overlays the gas sensing orifice  1   b  it is preferable for the membrane and cradle to include means of co-alignment such as notches (not shown). 
         [0053]    The probe is now connected to a means of power supply and data communication via cable  5 . The probe may be calibrated by placing a gas hood over the assembled probe, and presenting a suitable concentration of the analyte to the gas hood. Alternatively, the probe may be calibrated using an aqueous liquid, typically pure water, into which the gaseous analyte is dissolved. The former is generally preferable, and provides an advantage of using a gas-equilibrated, volatile-in-liquid detector over other volatile-in-water detection technologies. These previous detectors require aqueous reference samples, which are prone to loose the volatile as soon as their means of containment, typically a glass ampoule, is breached. 
         [0054]    Typically the cable  5  connected to the probe is flexible and armoured or sheathed so as to provide protection when submerged in a watery fluid, perhaps under very adverse conditions. The probe may include additional members to ensure to protect the assembly from damage, particularly the probe itself. It is however deleterious for the membrane  6  to be appreciably obscured from the aqueous environment presented to it, insofar as free flow of fluids across it is needed for dynamic sensing. 
         [0055]    The removal of the sensor may benefit from additional cradle members, not shown in  FIG. 1 , which enable the cradle walls surrounding the circular or cylindrical section of the gas sensor to be partly dismantled. 
         [0056]    The sensor shown in  FIG. 4  is best stored with its removable components removed from the sensor cradle  2 . The sensor may be manually assembled as described above, although in this case the membrane assembly shown in  FIG. 5  is affixed to the sensor cradle  2  only after careful orientation and assembly of gas sensor sub-components. For example, in the case of a PID sensor, a lamp is first inserted in the gas sensing member  11  opposite the membrane orifice  11   a.  Then the protective backing  14  to the adhesive section is removed. Then the membrane assembly is placed over the cradle wall flats  2   a  as shown in  FIG. 4  and pressed down to ensure a water tight seal. 
         [0057]    Following tests with the probe shown in  FIG. 4 , it is again advisable for the probe to be washed off in clean water and dried. The membrane  6  is peeled off cradle wall flats  2   a.  After removal of the sensor, the entire sub-assembly shown in  FIG. 5  is removable and disposable, being a small, environmentally benign and modest cost item. The sensor body can then be removed and stored in a separate storage capsule or refitted with a new membrane assembly as depicted in  FIG. 5 , ready for subsequent use. 
         [0058]    The instrument is calibrated as described above. In the case of a PID, the use of a gas for calibration is a particular advantage where the PID is being used to trace a volatile to which PID responds, with reasonable assurance as to the presence of that volatile. For example, it might be calibrated with 1 ppm xylene in air, using Henry&#39;s Law to determine the equivalent xylene-in-water concentration. 
         [0059]    Possible applications of the invention include, for example, remediation of polluted water, monitoring of potable water, food and drink processing, and regulatory enforcement.