The invention also relates to a method for operation of said device.

More in detail, the invention relates to a portable device of the said type, designed and made in particular to carry out a sampling and monitoring over time in indoor or outdoor environments, of organic contaminating compounds dispersed in the air, but also generally in gaseous fluids or liquids, by means of the SPME passive sampling technique, but which can be used for any place, where the detection of contaminating compounds dispersed in gaseous fluids and/or liquids is necessary.

The description below relates to a device placed in open environments for the sampling and monitoring over time of organic contaminating compounds dispersed in the air, but it is clear that it should not be considered limited to this specific use.

As is currently well known, the passive sampling technique known as SPME (Solid Phase Micro Extraction ) consists of using a solid substance, usually a particular type of coating attached to a fibre, to detect one or more gaseous or liquid phase analytes.

The fibre is usually retractable, stored inside a hollow needle, and then extracted and exposed to the sample to be analysed or immersed in it.

After a predetermined time interval necessary for the extraction, the fibre is withdrawn and the adsorbed analytes are then thermally desorbed by heating the fibre or by dissolution with solvents.

In particular, for the analysis of liquid and/or solid organic contaminating compounds which are placed in special glass tubes with a perforated cap called vials, the sampling of the contaminants takes place by exposing the fibre inside the vials in headspace mode, according to the prior art technique HS-SPME (Head Space - Solid Phase Micro Extraction), that is to say, in the air/vapour space between the liquid layer and the cap, or by direct immersion in the liquid, according to the prior art technique DI-SPME (Direct immersion - Solid Phase Micro Extraction).

The fibre consists of a metal core, or a glass core, that is, siliceous, coated with a polymeric film, or coating, which by chemical or physical affinity absorbs at ambient temperature the organic substances dispersed in the fluid with which it comes into contact.

These organic substances or contaminants remain attached until, by desorption at high temperature, for example approximately 250 °C, or by solubilisation in polar/nonpolar type organic solvents, the organic contaminants detach from the fibre to be detected by prior art analytical chemical techniques such as GC ( Gas Chromatography) or HPLC (High Precision Liquid Chromatography).

Moreover, this desorption process cleans the fibres and makes them active again for a subsequent sampling.

As is well known, the current SPME technique is manual, as it is necessary for an operator to manually expose the fibre in the environment whether closed or open, at a predetermined sampling point.

Currently, the SPME sampling technique is used in manual mode for in-situ sampling of the air, outdoor or indoors, of liquids for environmental surveys such as industrial/municipal waste, watercourses, urban waste disposal sites, and the like, in the chemical/food/cosmetic industry for the investigation of possible contaminants.

It is clear that this manual technique is difficult to use for monitoring contaminants over time, that is, during both day and night, as it would require the presence of an operator at the sampling site at all the hours set in the monitoring programme.

Moreover, this sampling technique requires that the analysis of the sample is performed as quickly as possible to avoid any desorption of the contaminants adsorbed in the fibre, which would cause possible loss of samples.

In light of the above, the aim of the invention to provide a device to automate the SPME sampling technique, so as to expose the fibres in an automatic and programmed manner over time.

Another aim of the invention is to provide a device which allows the desorption of contaminants to be limited, so as to preserve the collected sample.

Another aim of the invention is to provide a device which can be quickly and easily coupled to the prior art bench top instrumentation for analysis of the collected sample.

A further aim of the invention is to provide the instruments and the method of operation of said device.

The specific object of the present invention is therefore a device for the sampling of organic contaminating compounds dispersed in gaseous fluids and/or liquids comprising at least one sampling means comprising at least one fibre capable of moving from a retracted position, in which it is placed inside said sampling means, to an extracted position, in which it is immersed in said fluid, in order to detect said organic contaminating compounds, according to predetermined exposure times of said fibre in said fluid, said device comprising actuation means for moving said fibre from said retracted position to said extracted position and vice versa.

Further, according to the invention, said device may comprise a supporting member, provided with two or more housings, each configured to house a respective sampling means, and said actuation means are configured to move a fibre housed in a first housing from said retracted position to said extracted position and vice versa, and to move subsequently a fibre housed in a second housing from said retracted position to said extracted position and vice versa.

Again according to the invention, said device can comprise a logic control unit equipped with a program containing predetermined exposure times, capable of activating said actuation means to cause the exposure of said at least one fibre in said fluid for said predetermined exposure time intervals.

Preferably according to the invention, said logic control unit program controls the exposure times of all fibres contained in said housings. Further according to the invention, said supporting member and said actuation means are coupled in rotation with each other.

Again according to the invention, said supporting member comprises a fixed portion, a mobile portion equipped with two or more housings, able to rotate with respect to said fixed portion, a circular gearwheel integral with said mobile portion, in order to couple with said actuation means.

Preferably according to the invention, said actuation means comprise a first motor, equipped with a gearwheel, a second motor, a third motor, a first worm screw, coupled to said second motor, a second worm screw, coupled to said third motor, first lever, able to move along said first worm screw from a stroke start position to a stroke end position, and a second lever, able to move along said second worm screw from a stroke start position to a stroke end position.

Further according to the invention, said gear wheel of said first motor and said circular gear wheel of said movable supporting member are meshed together, so as to rotate said movable supporting member until reaching a predetermined position.

Again according to the invention, said device may comprise a sampling device comprising a hollow and elongated outer casing, comprising said sampling means, equipped with a first and a second end, capable of moving in a vertical direction from a raised to a lowered position, a spring, coupled to said outer casing, capable of being extended when said outer casing is in said raised position, and compressed when said outer casing is in said lowered position, and said sampling means may comprise a container, a plunger, slidably coupled to said container, a needle, located inside said container and containing said fibre, and a spring, coupled to said plunger for the escape of said fibre from said needle.

Preferably according to the invention, said first lever, in said stroke start position is distant from said first end of said outer casing, and in said stroke end position is in contact on said first end of said outer casing, for the escape of said needle from said container, and said second lever, in said stroke start position is distant from said plunger of said sampling means, and in said stroke end position is in contact on said plunger for the escape of said fibre from said needle.

Further according to the invention, each housing of said supporting member is provided with a watertight chamber comprising a containment structure, in which is made a through hole, a first membrane, placed beneath said through hole, a second membrane, placed beneath said first membrane, and a spacer element, placed between said first and second membranes.

Again according to the invention, said first and second membranes are made of elastic plastic material, which can be passed through by said needle.

Another object of the invention is a method of operation of a device for the sampling of organic contaminating compounds dispersed in gaseous fluids and/or liquids, comprising the following steps:

a. moving said first, second and third motors to an initial position; b. selecting the fibre to take the measurement;

c. extracting the tip of the needle corresponding to the selected fibre out of the device, at a predetermined speed;

d. exposing said selected fibre in the outside environment at a predetermined speed;

e. retracting said fibre inside said needle and said needle inside said device;

f. stopping said device for a predetermined period of time.

The invention is now described, by way of example and without limiting the scope of the invention, according to its preferred embodiments, with particular reference to the accompanying drawings, in which:

Figure 1 shows a front view of the portable device for the automatic sampling of organic contaminating compounds dispersed in gaseous fluids and/or liquids, according to the invention;

Figure 2 shows a perspective view from below of the device of Figure

1 ;

Figure 3 shows a front view of the device of Figure 1 , coupled to an external support;

Figure 4 shows a side view of the device of Figure 1 , without the cover casing;

Figure 5 shows a front view of a detail of Figure 4;

Figure 6 shows a front perspective view of a component of the device shown in Figure 5;

Figure 7 shows a top view of the component of the device shown in Figure 6;

Figure 8 shows a top view of the component of the device shown in figure 5, equipped with drive motors;

Figure 9 shows a view from below of the component shown in Figure

8;

figure 10 shows a front section view of another component of the device shown in Figure 5;

Figure 11 shows a front perspective view of the component shown in Figure 10;

Figure 12 shows a front view of a detail of Figure 10;

Figure 13 shows a schematic front view of a portion of the component shown in Figure 10;

Figure 14 shows a front view of the component shown in figure 10, in a first position;

Figure 15 shows a front perspective view of the component shown in Figure 14, in a first position;

Figure 16 shows the detail of Figure 5, in a first position;

Figure 17 shows a perspective view from below of the device shown in Figure 4, in a first position;

Figure 18 shows a front view of the component shown in Figure 10, in a second position;

Figure 19 shows a front perspective view of the component shown in Figure 14, in a second position;

Figure 20 shows the detail of Figure 5, in a second position;

Figure 21 shows a perspective view from below of the device shown in Figure 4, in a second position;

Figure 22 shows a front view of the component shown in Figure 10, in a third position; Figure 23 shows a front perspective view of the component shown in figure 14, in a third position;

Figure 24 shows the detail of Figure 5, in a third position;

Figure 25 shows a perspective view from below of the device shown in Figure 4, in a third position.

The similar parts will be indicated in the various drawings with the same numerical references.

With reference to Figures 1 to 5, the device D for the automatic sampling of organic contaminating compounds dispersed in gaseous fluids and/or liquids, which is the object of the invention, essentially comprises a support base 1 , a cover casing 2, a movable supporting member 3, at least one sampling element 4 for the sampling of organic compounds, coupled to said supporting member 3, means 5 of actuation of said at least one sampling element 4 and of said supporting member 3, and a logic control unit, located inside said device D, not shown in the drawings, in which the operating program of said device D is stored.

In particular, said support base 1 for device D comprises a first 1 _a and a second 1 b portion and a lower surface 1 1 , beneath said first 1 _a and second 1 b portion.

A through hole 12 through which a part of said sampling element 4 passes, as will be described in detail below, is made on said lower surface 1 1 .

Said hole 12 has a diameter of approximately 2 mm.

Referring in particular to Figure 13, at said through hole 12, inside said base 1 , there is a watertight chamber 14 of which all the housings included in the supporting member 3 are provided.

Said watertight chamber 14 has a volume, within a range of 0-100 micro-litres, which is variable according to the structure of the silicone baffle.

The purpose of said watertight chamber 14 is to limit the desorption of the sampled substances so that chemical analysis can be carried out after

24 or 48 hours without substantial loss of sample.

In particular, said watertight chamber 14 comprises a containment structure 141 , in which is made a through hole 141 _a , a first membrane 142, placed beneath said through hole 141 a, a second membrane 143, placed beneath said first membrane 142, and a spacer element 144, placed between said first 142 and second 143 membranes.

Said first 142 and second 143 membranes are made of elastic plastic material, for example rubber or silicone, which can be easily passed through, in and out, by the tip of a needle, without permanent perforations, therefore not closable.

In addition, a coupling plate 13 is fixed on said lower surface 1 1 in order to realize the coupling between said device D and other laboratory instruments external to the device D itself.

As shown in figure 3, said device D can also be installed on an external support S, by means of a fixing bracket F.

Said supporting member 3 is placed in said first portion 1 _a of said base 1 , a battery B is placed in said second portion 1 b of said base 1 and said actuation means 5, which are substantially placed between said supporting member 3 and battery B.

With reference to Figures 6 and 7, said supporting member 3 comprises a fixed portion 31 , coupled to said base 1 and a movable portion 32, coupled in rotation to said fixed portion 31.

A plurality of housings 32 _a ,b,...,k,...n are made in said movable portion

32 and there is a circular gearwheel 33, designed to couple with said actuation means 5, as described in detail below.

Said plurality of housings 32 _a ,b,...,k,...n may have a variable number.

In this embodiment, thirteen housings are made in said supporting member 3, so as to carry out a predetermined number of sampling operations distributed over a predetermined period of time, for example one sampling every two hours.

Each housing of said plurality of housings 32 _a ,b,...,k,...n houses a sampling element 4.

With reference to Figures 10 to 13, said sampling element 4 essentially comprises a hollow and elongated outer casing 41 , a spring 42 extending along the entire surface of outer casing 41 and a sampling means 43 or SPME holder, placed inside said outer casing 41. Said outer casing 41 is equipped with a first 41 _a and a second 41 b end.

At said first end 41 _a , a blocking element 44 is placed, inside said outer casing 41 , to block said sampling means 43, when inserted in said outer casing 41.

Whilst a contact element 45 is located at said first end 41 _a outside said outer casing 41.

Said outer casing 41 is able to move in a vertical direction to move from a raised position with respect to the housing 32k, in which said spring 42 is extended, to a lowered position, wherein it is placed partially or totally inside said housing 32k and wherein said spring 42 is compressed and said contact element 45 is in contact at the top of said housing 32k.

With reference to Figure 12, said sampling means 43 or SPME holder is of known type and comprises an elongated, substantially cylindrical container 431 equipped with a first end 431 _a and a second end 431 b.

A 432 needle is placed inside said container 431 , designed to slide inside said container 431 and comprising inside it an SPME fibre 432'.

Said 432 needle has a first 432 _a and a second 432b end.

At said first end 432 _a is coupled a return spring 433 of said fibre 432', whilst from said second end 432b comes out said fibre 432', as described in detail below.

Said sampling means 43 also comprises a plunger 434 slidably coupled to said container 431 , and able to compress said spring 433 for the escape of said fibre 432' from said needle 432.

With reference now to Figures 5, 8 and 9, said actuation means 5 essentially comprise a first motor 51 , a second motor 52, a third motor 53, a first worm screw 54, coupled to said second motor 52, a second worm screw 55, coupled to said third motor 53, a first lever 56, coupled to said first worm screw 54, a second lever 57, coupled to said second worm screw 55, a first safety switch 58, coupled to said first worm screw 54 and a second safety switch 59, coupled to said second worm screw 55.

Said first lever 56 is able to move along said first worm screw 54 from a stroke start position, in which it is distant from said first end 41 _a of said outer casing 41 , to a stroke end position, in which it is in contact with said first end 41 _a .

Said second lever 57 is also able to move along said second worm screw 55 from a stroke start position, where it is far from said plunger 434 of said sampling means 43, to a stroke end position, where it is in contact with said plunger 434.

Said first motor 51 is equipped with a gearwheel 51 1.

Said gear wheel 51 1 of said first motor 51 and said circular gear wheel 33 of said movable supporting member 3 are meshed together to form a gearing, so as to rotate said movable supporting member 3 until reaching a predetermined position.

Said second motor 52 is able rotate said first worm screw 54, translating the axial motion into linear motion, so as to move said first lever 56 up and down along said first worm screw 54.

In the descent step, said first lever 56 is able to exert a thrust force on said first end 41 _a of said outer casing 41 , downwards.

Said third motor 53 is able rotate said second worm screw 55, translating the axial motion into linear motion, so as to move said second lever 57 up and down along said second worm screw 55.

During the descent step, said second lever 57 is able to exert a thrust force on said plunger 434 which, in turn, exerts a thrust force on said return spring 433 which causes said SPME fibre 432' to escape from said needle 432, as described in detail below.

Said first 51 , second 52 and third 53 motors are

servomotors of digital type and each one is equipped with a microprocessor programmed to drive the motor itself and precisely control its position by means of a feedback circuit, a position sensor and a known algorithm of PID (Proportional Integral Derivative) type.

The operation program of each servomotor can be modified from outside using a USB-type connection module.

Said first 58 and second 59 safety switches are mechanical switches which are pressed when a predetermined end of stroke position is reached.

Said device D has dimensions of approximately 40x20 cm and a height of 30 cm, and has a weight of less than 10 kg and is made externally in aluminium.

Said actuation means 5 move according to the instructions sent by said logic control unit, according to the predetermined program.

Said logic control unit can also interface with external sources which are able to modify the steps of said predetermined program, contained in said logic control unit.

Said device D comprises an RTC - Real Time Clock which turns on said device D at predetermined time intervals and then it turns off after the programmed measurement.

The device D is also equipped with a USB connection module.

The operation of the device D for the automatic sampling of organic contaminating compounds dispersed in gaseous fluids and/or liquids, which is the object of the invention, as described above is carried out as follows.

With reference in particular to Figures 14 to 25, when it is necessary to carry out automatic sampling of organic compounds dispersed in a predetermined fluid by means of said device D, this is activated.

Initially, said movable supporting member 3 is stationary, said one or more sampling elements 4 housed, in corresponding number, in said plurality of housings 32 _a,b, ...,k,....n are in the extracted position with respect to said plurality of housings 32 _a,b, ...,k,...n, said needle 432 is in said watertight chamber 14 and said fibre 432' is inserted in said needle 432.

The default program contained in said logic control unit controls the drive of said first motor 1.

In a first step, said first motor 1 rotates said movable gearwheel 33, so said movable portion 32 rotates with respect to said fixed portion 31 , until a predetermined housing 3k of said plurality of housings 32 _a,b, ...,k,...n reaches said watertight chamber 14.

In a second step, said second motor 52 rotates said first worm screw 54, translating the axial motion into linear motion, so as to move said first lever 56 down along said first worm screw 54.

In the descent step, said first lever 56 exerts a thrust force on said first end 41 _a of said outer casing 41 , downwards, pushing said outer casing 41 downwards, so that said needle 432 perforates said first membrane 142.

Said needle 432 remains between said first 142 and second 143 membrane for a predetermined time.

Subsequently, said first lever 56 continues to move to the stroke end position, causing the perforation of said second membrane 143 by said needle 432 which escapes from said device through said through hole 12.

In a third step, said third motor 53 rotates said second worm screw 55, translating the axial motion into linear motion, so as to move said second lever 57 down along said second worm screw 55.

During the descent step, said second lever 57 exerts a thrust force on said plunger 434 which, in turn, exerts a thrust force on said return spring 433 which causes said SPME fibre 432' to escape from said needle 432, when said lever 57 has reached the end of stroke position.

Said SPME fibre 432' remains exposed in the sampling environment for a predetermined time.

At the end of the exposure time of said SPME fibre 432', determined by the program contained in the logic control unit, said SPME fibre 432' is retracted inside said needle 432' which withdraws inside said watertight chamber 14.

The exposure speed of said SPME fibre 432' can be set by the logic control unit and can allow the exposure of said fibre 432' with a speed in the order of magnitude of millimetres per minute or all together with a speed of approximately 10 mm per second.

However, the choice of exposure speed depends on the type of contaminating substance to be sampled in the sampling environment or whether spot or time-averaged sampling is to be performed.

Subsequently, all the components of said device D return to the rest position making movements opposite to those just described.

In particular, said third motor 53 turns in the opposite direction with respect to the previous one, said second worm screw 55 rotates in the opposite direction, said second lever 57 returns to the stroke start position and said return spring 433 recalls said fibre 432' in said needle 432.

Subsequently, said second motor 52 turns in the opposite direction with respect to the previous one, said first worm screw 54 rotates in the opposite direction, said first lever 56 returns to the stroke start position and said spring 42 recalls said needle 432 in said watertight chamber 14.

Finally, said first motor 51 turns in the opposite direction to the previous one and returns to the initial position, until it receives a new pulse to bring a housing 32k of said plurality of housings 32 _a ,b,...,k,...n to said through hole 12.

The movement of said plurality of housings 32 _a ,b,...,k,...n is determined by a sequence, not necessarily ordered from one to thirteen, stored in said control program.

The logic control unit is equipped with a program for the operation of said device D.

The operating steps of the programme are as follows:

a. Resetting step

The microprocessor of the logic control unit returns said first 51 , second 52 and third 53 motors to the initial position stored in the program; b. Step for selecting SPME fibre 432' to be used to perform the measurement;

c. Step for extracting the tip of the needle 432', within which the selected SPME 432' fibre is located, to the outside of device D, at a predetermined speed;

d. Step for exposing the SPME fibre 432' to the outside environment at a predetermined speed;

e. Step for retracting the SPME fibre 432' inside the needle 432 and the needle 432 inside the device D;

f. Sleep step of the duration of a predetermined time interval, in which said device D does not perform any movement;

g. Shutdown step wherein said device D is in a stand-by mode. Additional secondary functions are used to select date and time to wake up the device D, to read and write parameters from the microprocessor's non-volatile memory, and the like.

When a program is started, the microprocessor performs the following steps: