DEVICE AS A SYSTEM OF MODULES FOR SAMPLING, PRE-CONCENTRATION AND ANALYSIS OF EXPLOSIVES IN AQUEOUS SOLUTIONS AND / OR UXO AND MUNICIPAL CONTAMINATIONS IN THE SEA AND ON THE SEABOTTOM, AS WELL AS METHOD FOR THIS

Description

[0001] The invention relates to a device as a system of modules for sampling, pre-concentration and analysis of explosives in aqueous solutions, in particular of UXO and munitions legacy in the sea and on the seabed, and a method directed thereto.

[0002] Explosives are chemical compounds or mixtures of chemical compounds that can react very quickly under certain conditions, releasing a large amount of energy.

[0003] For the purposes of the invention, a device as a system is understood to be a composite whole arranged in modules from several technical parts, consisting of different components with different technical properties, which are considered as a common whole due to certain ordered relationships among themselves.

[0004] The inventive device, as a system of modules for sampling, pre-concentration, and analysis of explosives, comprises an ex situ module for sampling and pre-concentration. An external module for in situ sampling and pre-concentration can be connected to the ex situ module. The inventive device as a system is thus flexibly designed for all types of sampling, pre-concentration, and analysis of explosives in aqueous solutions.

[0005] The method describes process steps for sampling, analysis and treatment by the inventive device as a system of modules for sampling, pre-concentration and analysis of explosives.

[0006] To clarify the invention, the terms and acronyms used in the present invention are defined as follows: UXO In various regions of the world's oceans, war materiel has been sunk during and after armed conflicts; this material is known as duds or Unexploded Ordnance or UXO be designated.

[0007] TNT is an explosive compound that is generally Trinitrotoluene or TNT. The compound is produced by the nitration of toluene using nitrating acid, a mixture of nitric and sulfuric acid. TNT was first described in 1863 by Julius

[0008] Wilbrand (1839-1906) synthesized TNT. Since 1901, TNT has been produced and used on a large scale. The so-called TNT equivalent serves as a measure of the energy released in an explosion.

[0009] RDXis an explosive compound commonly known as hexogen, cyclotrimethylenetrinitramine, cyclonite, T4 or Research Department Explosive or Royal Demolition Explosive, short RDX) RDX is a highly explosive, toxic substance from the nitramine group, which was produced in large quantities during the Second World War and is still in use today. RDX was patented in 1898 by the Berlin chemist and pharmaceutical entrepreneur Georg Friedrich Henning as an explosive for technical applications (DE 104 280 A).

[0010] ADNT is the compound 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene. These are primary reduction and microbial degradation products of the military explosive 2,4,6-trinitrotoluene (TNT). ADNT forms relatively quickly when TNT is released and is capable of persisting in the environment.

[0011] DNB is an explosive compound that is generally Dinitrobenzeneor DNB and is classified as a base substance for substitute explosives.

[0012] ESI-MS is a device for analysis using the Electrospray ionization Mass spectrometry or ESI-MS or ESMS. ESI-MS is an ion generation technique known since 1968 and used in mass spectrometry. This technique has the advantage of generating ions at atmospheric pressure and is a preferred ionization method for the analysis of biomolecules. ESI-MS is used to determine molecular masses, analyze and sequence proteins and oligonucleotides, and quantitatively determine the concentrations of drugs, pesticides, and explosives, even for relatively small molecules.

[0013] UV-S is a device for analysis using the UV spectrophotometry or UV-S.UV-S is a spectroscopic method of optical molecular spectroscopy that uses electromagnetic waves of ultraviolet (UV) light.

[0014] HPLC is a device for use in the High-pressure liquid chromatography or HPLC. HPLC pumps Their function is to promote ion exchange in a sample with a constant flow against high pressure. They should operate with low pulsation and dead volume, exhibiting high long-term stability and reliability, so that qualitative and quantitative analyses can be derived from the detector signals.

[0015] ACN is an organic laboratory solvent. Acetonitril or ACN It is also used as a solvent in NMR spectroscopy in conjunction with mass spectrometry, IR spectroscopy and UV / VIS spectroscopy.

[0016] The development of offshore resources and the environmental protection of the seas are hampered by the presence of UXO and unexploded ordnance in the sea and on the seabed. In addition to the explosion and safety risks, this munitions contain cytotoxic, genotoxic, and carcinogenic chemicals associated with conventional explosives, chemical warfare agents, and munition components.

[0017] Clearing underwater munitions is very dangerous due to the hazards associated with accidental detonation and the release of toxic chemicals.

[0018] A number of explosives analysis systems are known from the state of the art, e.g. for use in baggage screening at airports or in access control, but these are unsuitable for offshore use.

[0019] Publication US 2004 / 0101900A1 discloses an assay for the detection and quantification of TNT and TNT-related compounds in aqueous solutions, including seawater, containing a TNT analogue bound to a TNT detection element. A measurable change in property, such as a decrease in the fluorescence emission intensity of the TNT analogue, occurs when a test sample containing TNT or related compounds is added to the assay, causing free TNT to displace the TNT analogue from the TNT detection element. The associated method for the detection and quantification of TNT and TNT-related compounds is also disclosed.

[0020] Publication US 2016 / 0011154A1 discloses HPLC methods for the detection, identification, and quantification of munitions compounds or munitions materials. Insensitive munitions explosives (IMX) can be detected together with conventional munitions compounds such as 2,4,6-trinitrotolene (TNT) in a single column analysis. The methods are also suitable for the analytical evaluation of soil samples, aqueous samples such as groundwater samples, and tissue samples containing insensitive munitions explosives (IMX).

[0021] The publication RUSSELL, AL [et al.]: Analysis of munitions constituents in IMX formulations by HPLC and HPLC-MS. In: Talanta, Vol. 128, 2014, pp. 524-530 further states that the use of sensitive munitions explosives (IMX) is increasing as the Army seeks to replace certain conventional munitions components, such as 2,4,6-trinitrotoly (TNT), to enhance safety. The IMX formulations are more stable and therefore less prone to accidental detonation, while simultaneously being designed to match the performance of previous materials. Two formulations, IMX 101 and 104, are being investigated as replacements for TNT in the Army's Composition B artillery shells and mortars, respectively.The chemical formulations of IMX-101 and 104 consist of four components: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), 1-nitroguanidine (NQ), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), which are mixed in different ratios to achieve the desired effect. This paper describes the analysis of the components using single-column HPLC-UV-ESI-MS. The determined limits of detection are consistent with similar HPLC analyses of compounds and range between 7 and 9 µg / L. Gradient mobile phases are used to enable the separation of the four target compounds in more complex mixtures of other accompanying compounds. Mass spectra are used to confirm the identity of the analyte with the chromatographic retention time.

[0022] In US patent application 2004 / 0235187 A1, an instrument for sampling and analyzing analytes in a liquid sample is disclosed. A liquid sample is pre-concentrated using a chromatographic column before being analyzed in a two-stage analyzer. A high-performance liquid chromatography system with ultraviolet detection can be used in conjunction with electrochemical detection for the analysis of environmental contaminants, including explosive residues. The present invention also enables the on-site analysis of such contaminants. The present invention also provides methods for analyzing the components of a liquid sample, including methods for on-site analysis.

[0023] The currently available and mature geophysical technologies for the non-destructive measurement of physical or chemical anomalies are not currently capable of universally identifying munitions on the seabed.

[0024] The present invention eliminates the shortcomings of the prior art.

[0025] The present invention is based on the objective of providing, through sampling, a direct detection of explosive material with a unique signature for objects that need to be cleared in order to prevent the release and chemical contamination of the sea by munitions.

[0026] Another objective of the invention is to provide a near real-time detection technology for chemical substances, also in situ.

[0027] Another task is to analyze several chemical compounds simultaneously and to detect specific evidence of dissolved explosives and chemical warfare agents in seawater.

[0028] Another task is to provide a seagoing device for detecting chemicals associated with unexploded ordnance in the marine environment.

[0029] The inventive device, as a system of modules for sampling, pre-concentration and analysis of explosives, is intended to be used as a device for supporting munitions detection technology in combination with existing mature geophysical technologies, in order to provide, in combination with known sensors, a probability of detection and better information for the characterization of explosives and chemical warfare agents in seawater.

[0030] The task is explained in the unpublished EU project ExPloTect (ExPloTect: "Ex-situ, near-real-time exPlosive compound detection in seawater") of the European Maritime and Fisheries Fund, project number: 863693, https: / / www.explotect.eu as follows: The project ExPloTect: "Ex-situ detection of explosive compounds in seawater in near real-time, addresses problems of the Development of offshore resources and the associated environmental protection in the presence of UXO and relic munitions on the seabed. In addition to the explosion and safety risks, this munitions contain cytotoxic, genotoxic, and carcinogenic chemicals associated with conventional explosives, chemical warfare agents, and munition structural components. Due to the dangers associated with accidental detonation and the release of toxic chemicals, there is a critical need to clear underwater munitions.

[0031] SolvedThis task is accomplished with the inventive device as a system of modules for sampling, pre-concentration and analysis of explosives, as well as a method for sampling, sample analysis and sample treatment.

[0032] The device is designed as a system of modules for sampling, pre-concentration and analysis of explosives in aqueous solutions and / or UXO and unexploded ordnance in the sea and on the seabed, wherein The device as a system comprises at least a housing in which at least one first liquid system module and / or one second liquid system module and at least one analysis system module are provided, with the following components in the first liquid system module: at least three HPLC pumps with different pumping capacities; at least two valves; at least one sample selection valve, as a 6-way valve with controllable setting options for waste and injection positions; at least one inline filter; with the following components in the second liquid system module: at least one HPLC pump; at least one electronic control board; and with the following components in the analysis system module: at least one mixer; at least one valve, as a diverter valve; at least one HPLC column heater; at least one UV system with capillary waveguide and spectrophotometer;characterized in that the first liquid system module comprises at least one syringe pump with a 4-port distribution valve, and the at least two valves have controllable transfer and charging / injection positions; the analysis system module comprises at least one ESI-MS; the second liquid system module comprises a pressure housing; a first pressure housing end cap A; a second pressure housing end cap B; at least one HPLC column selector, with at least two HPLC columns, as solid-phase extraction columns for sampling; in the case of a second liquid system module, at least one of the pressure housing end caps has connecting elements that detachably connect the second liquid system module to a respective analysis system module.

[0033] According to the procedure, the method for sampling, sample analysis and sample treatment with a device according to the invention is designed as a system comprising at least the following steps: a. Pre-cleaning (100) b. Sample loading (101) c. Transfer (102) d. Final sample preparation (103) e. Chromatographic separation (104) f. Mass spectrometry (MS) detection (105) g. Spectrophotometric detection in the ultraviolet (UV) range (106) h. Post-cleaning (107).

[0034] Furthermore, each subsequent sample or discrete sample of a sampling process can be loaded onto the first SPE column (9) upon reaching a first sample in step c. Transfer.

[0035] The device, a system of modules for sampling, pre-concentrating, and analyzing explosives in aqueous solutions, particularly UXO and unexploded ordnance in the sea and on the seabed, and a method designed for this purpose, performs direct sampling (ex situ and / or in situ), sample concentration, and analysis of explosive compounds (TNT, RDX, ADNT, DNB) from seawater. The target compounds are separated by HPLC and detected in the analysis module by electrospray ionization mass spectrometry (ESI-MS) and UV spectrophotometry.

[0036] The first liquid system module enriches large-volume seawater samples (up to at least 1 L) using a two-column elution-dilution process to achieve a 5000-fold enrichment factor. Switching valves and sample loops are employed to keep column purge times short and reduce interfering compounds. A syringe pump is used to inject standard solutions for calibration.

[0037] The pre-concentrated sample is separated using HPLC, with a switching valve eliminating unwanted organic compounds. The sample stream is then split between the ESI-MS and UV detectors for dual detection in the analysis module. The system is fully automated from sample collection to data analysis and currently requires less than 15 minutes per sample.

[0038] The second liquid system module, unlike the first liquid system module, works with sampling and pre-concentration in situ, and is therefore an independent underwater device for sampling and pre-concentration of dissolved explosives in seawater directly at the UXO and relic munitions.

[0039] The second liquid system module essentially performs step 101 of the first liquid system module, but can collect up to ten samples during a single run. It consists of an HPLC pump and an HPLC column selector housed in a watertight pressure case. The samples are filtered and sequentially pre-concentrated by pumping them through a series of ten solid-phase extraction (SPE) columns. The pump and column selector are controlled by an electronic circuit board via switching the power supply on and off. The second liquid system module is directly connected to the analysis module, and the collected samples are then analyzed by the analysis module, processed using the associated software, and displayed on a screen.

[0040] The invention is described below with reference to the accompanying illustrations. Image descriptiondescribed, whereby these are intended to explain the invention and are not to be considered limiting: They show: Fig. 1 shows an exemplary device as a system in sectional view with the components of the modules first liquid system module 4 and analysis system module 22 without the second liquid system module 30 (see also Fig. 4 ); Fig. 2 Example screenshots from a data display on the external computer with display 21 of an evaluation software (native software) for a seawater sample, a measurement with the analysis system module 22 according to Fig. 1Fig. 3 shows exemplary procedure steps for the execution of a measurement with a device as System 1; Fig. 4 shows an exemplary second liquid system, Module 30. The structure of Module 30 is shown in longitudinal section (figure above) and in a top view of the pressure housing end cap A and pressure housing end cap B; Fig. 5 shows an exemplary device as System 1 in perspective view with the modules of the system: the first liquid system, Module 4; the analysis system, Module 22; and the second liquid system, Module 30. For the sake of completeness, the external components—external air compressor / nitrogen generator Module 2, external computer with display 21, and an external waste canister 28—are also shown.

[0041] Fig. 1Figure 1 shows an exemplary device as System 1 in sectional view with the components of the first liquid system module 4 and the analysis system module 22. The second liquid system module 30 of the device as System 1 is omitted for clarity. Fig. 4 shown and explained further below.

[0042] The exemplary device, designated as System 1, shows modules 4 and 22 in a sectional view, including the components of a first liquid system module 4 and an analysis system module 22, housed in an enclosure 3. Modules 4 and 22 are suitable for installation in a standard 19" electronics rack enclosure 3, but can also be adapted to other structural requirements. For on-site or shipborne use, the 19" electronics rack enclosure is preferably installed in a portable, robust 19" rack-mount enclosure. The first HPLC pump 5 has a high pumping capacity, e.g., a maximum capacity of 500 ml / min, with a titanium pump head and control via proprietary software. The second HPLC pump 14 and the third HPLC pump 15 have lower pumping capacities, e.g., a maximum capacity of 10 ml / min each, and are also controlled by proprietary software.The first valve 10 and the second valve 11 each have transfer and loading / injection positions controlled by the system's software. The sample selection valve 6 is a six-way valve with adjustable settings for waste and injection positions and is controlled by the system's software. Sample selection valve 6 allows the user to choose between online sample streams or discrete sample streams. The setting is manually controlled at the start of a sampling run and then remains in effect until further control is required, for example, for measuring a discrete sample, or is terminated after the entire online sample series has been completed. Online samples are taken, for example, from the ship's pumped seawater (pure seawater or engine cooling water) or from a pump mounted on the ship's hull. The inline filter 13 preferably consists of a sintered stainless steel filter with a 5 µm pore size.The syringe pump 16 with 4-port distribution valve 17 preferably has a 1 mL syringe and is controlled by the system's own software. The ultra-compact HPLC column heater 25 maintains the HPLC column at the set temperature, preferably 40 ± 0.05 °C. The respective UV system 24 preferably has a xenon light source with a 1 m capillary waveguide and a spectrophotometer, such as a PX-2 pulsed xenon lamp and a FLAME-S UV-VIS spectrometer (Ocean Insight). A well-known product, such as a Microsaic MiD® < 4500 from Microsaic Systems, is used as the compact ESI-MS instrument.

[0043] The exemplary device, as System 1, is supplied as needed with high-purity, compressed nitrogen from an external air compressor / nitrogen generator module 2, which is housed in a separate portable, robust enclosure, preferably designed as a 19" rack, as shown in Fig. 5 shown schematically.

[0044] The Fig. 2 shows exemplary screenshots from a data display of a measurement on an external computer with display 21 with the inventive device as system 1 of modules for pre-concentration and analysis (4 or 30, 22) of explosives by an evaluation software (in-house software) for a seawater sample to which 25 ng of an explosive target compound were added.

[0045] From top to bottom: the first curve shows a measurement curve of a "neutral" sample with ESI-MS of mass 236.1 amu (stable-isotope labile TNT), as an internal standard, with a sample to which no internal standard was added; the second curve is a measurement of a sample with ESI-MS with a peak of ADNT; The third curve is a measurement of a sample with ESI-MS with a peak of TNT; the fourth curve a measurement of a sample with ESI-MS with a peak of RDX; and the fifth curve a measurement of a sample with UV-Swith a peak of DNB. The low peaks in the UV-S curve represent unknown natural organic compounds. Each peak is marked by an arrow. The curves also show good peak separation relative to each other.

[0046] Fig. 3 shows by way of example the process steps of a measurement with the inventive device as system 1 of modules for pre-concentration and analysis (4 or 30, 22) of explosives (according to Fig. 1 or 4). Step 1: Pre-cleaning 100: Valves 10 and 11 are in the transfer position. The third valve (diversion valve) 26 is moved to a waste position. Solid-phase extraction columns 9 and 12 are cleaned with 80% acetonitrile (ACN) by the third HPLC pump 15. The spent ACN is backwashed through the inline filter 13 and then diverted via the third valve (diversion valve) 26 into the hazardous waste collection in the external waste canister 28. Step 2: Sample loading 101: Valves 10 and 11 are moved to the load / injection position. The sample selection valve 6 is set to either online or discrete sample flow. The sample is pumped with seawater through the first HPLC pump 5. Simultaneously, either internal or external standards are added to the sample stream via the syringe pump 16 and its integrated 4-port distribution valve 17. Particles in the sample are removed by the inline filter 13.The sample passes through the sample SPE column, first solid-phase extraction column 9. The explosive target compounds are retained on the sample SPE column, first solid-phase extraction column 9. The outflowing seawater is discharged back into the sea, e.g., over the ship's side or through a drain pipe. Step 3: Transfer 102: Valves 10 and 11 are moved to a transfer position. The third valve (diversion valve) 26 is moved to the waste position. The analytical column, first solid-phase extraction column 9, is flushed with ultrapure water from the reagent container 20 via the second HPLC pump 14. Then, ACN from the reagent container 19 is pumped via the third HPLC pump 15 to elute the target compounds from the sample SPE column, first solid-phase extraction column 9.The ACN stream containing the target compounds is diluted online with ultrapure water, and the compounds are retained on the analytical column, second solid-phase extraction column 12. Particles from the inline filter 13 are backwashed with the wastewater and discharged via the third valve (diversion valve) 26 into the hazardous waste collection, e.g., an external waste canister (28).

[0047] The next subsequent sample or discrete sample is loaded simultaneously onto the first SPE column 9 in this phase, i.e. in step 3, transfer 102. Step 4: Final Sample Preparation 103: Valves 10 and 11 are set to the Load / Inject position. The third valve (diverter valve) 26 is set to the Waste position. The target compounds are eluted from the analytical column, second solid-phase extraction column 12, with ACN pumped via the third HPLC pump 15. The ACN stream is diluted online with ultrapure water pumped via the second HPLC pump 14 and the mixer 23 to achieve an ACN concentration (36%) required for chromatographic separation and analysis with the ESI-MS mass spectrometer 27. Step 5: Chromatographic Separation 104: The target compounds in 36% ACN are pumped through a C8 HPLC column maintained at 40 ± 0.05°C in an ultracompact column heater 25. Organic non-target compounds that elute first from the chromatography column are diverted via the third valve (diversion valve) 26 into the hazardous waste collection, e.g.an external waste canister (28) is diverted. The third valve (diversion valve) 26 is then switched again, and the HPLC column outflow containing the target compounds is diverted to the mass spectrometer inlet of the ESI-MS 27. The compounds are separated within 10 minutes in the following order: RDX, DNB, ADNT, TNT. Step 6: Mass Spectrometry (MS) Detection 105: For MS detection, a compact Microsaic MiD®< 4500 electrospray ionization mass spectrometer is used as the ESI-MS 27 in this example. The sample flow is divided, with 1 µl / min entering the detector and the remaining 999 µl / min being diverted to the outlet. Only RDX, ADNT, and TNT are suitable for MS detection, as DNB is poorly ionized. The target compounds are analyzed in single-ion mode (SIM) at the following masses: TNT: 226.1 m / z; RDX: 257.0 m / z, 259.0 m / z; ADNT: 196.0 m / z. 7.Step 1: Spectrophotometric detection in the ultraviolet (UV) range 106: The sample outlet of the ESI-MS 27 is directed into a 100-cm waveguide cell with a xenon light source. The absorption at 254 nm is measured with a spectrophotometer. UV detection is primarily required for DNB, but can also be used for the other target compounds. Step 8: Post-cleaning 107: Valves 10 and 11 are moved to the loading / injection position. The third valve (diverter valve) 26 is moved to the injection position. The solid-phase extraction columns 9 and 12 are cleaned with 80% acetonitrile (ACN) by the HPLC pump 15.

[0048] Fig. 4 Figure 31 shows an example of the structure of the second liquid module 30 in longitudinal section (figure above) and in top view of the pressure housing end caps A and B 31, 37.

[0049] The longitudinal section of the tubular pressure housing 34 shows an HPLC column selector 32 with ten HPLC columns 33, solid-phase extraction columns for sampling. Furthermore, an HPLC pump 36 (capacity up to 500 ml / min) and an electronic control board 35 are installed in a pressure-resistant manner.

[0050] The pressure housing end cap A 31 incorporates an inlet connection to the analysis system module 38 and a water outlet / drain to the analysis system module 40. The pressure housing end cap B 37 incorporates a pump outlet to the T-filter 41, a sample water inlet / pump inlet 42, a sample inlet from the T-filter to the column selector 43, a power / communication connection (e.g., a SubConn® connector), and a T-filter (preferably 5 µm).

[0051] In the example, two transport handles 39 are attached to the pressure housing end caps A and B 31, 37 for easy, safe handling.

[0052] Analogous to the one in Fig. 3In the second liquid module 30, the following process steps take place according to the sequence shown: In step 101: The sample water is pumped through the pressure housing end cap B 37 via the sample water inlet / pump inlet 42 into the HPLC pump 36. The sample is pumped from the pressure housing end cap B 37 through the pump outlet to the T-filter 41, through the T-filter 45, and via the sample inlet from the T-filter to the column selector 43 in the pressure housing 34. The sample is passed through the HPLC column selector 32 and through the HPLC columns 33. The outflowing seawater leaves the device through the water outlet / drain 40 to the analysis system module at the pressure housing end cap A 31. The ten HPLC columns 33 are selected sequentially, and the switching of the HPLC column selector 32 and the pump operation are controlled by switching the power supply on and off via the power / communication link 44 and the electronic control board 35.

[0053] In step 102: The samples collected with the second liquid module 30 are analyzed by connecting the inlet connection to the analysis system module 38 and the water outlet / drain 40 to the analysis system module. Then the power / communication connection 44 is connected to the analysis system module, and the samples can be analyzed, evaluated, and displayed via the subsequent steps 103 to 107.

[0054] Fig. 5 shows an example of the structure of a Device as System 1 of the first liquid system module 4 and the analysis system module 22 with the second liquid system module 30 and the external components: air compressor / nitrogen generator module 2, waste canister 28 and computer with display 21. Reference symbol list

[0055] 1 Device as a system 2 External air compressor / nitrogen generator module 3 Housing 4 First liquid system module 5 First HPLC pump 6 Sample selection valve 7 Incoming seawater 8 Outgoing seawater 9 First solid-phase extraction column 10 First valve 11 Second valve 12 Second solid-phase extraction column 13 Inline filter 14 Second HPLC pump 15 Third HPLC pump 16 Syringe pump 17 4-port distribution valve 18 Reagent container holder 19 ACN reagent container 20 Ultrapure water reagent container 21 External computer with display 22 Analysis system module 23 Mixer 24 UV system 25 HPLC column heater 26 Third valve (diversion valve) 27 ESI-MS 28 External waste canister 30 Second Liquid system module 31 Pressure housing end cap A 32 HPLC column selector 33 HPLC columns (10 solid-phase extraction columns) 34 Pressure housing 35 Electronic control board 36 HPLC pump (up to 500 ml / min) 37 Pressure housing end cap B 38 Inlet connection to the analysis system module 39 Carrying handle 40 Water outlet / drain to the analysis systemModule 41 Pump outlet to T-filter 42 Sample water inlet / pump inlet 43 Sample inlet from T-filter to column selector 44 Power / communication connection 45 T-filter (preferably 5 µm) 100 Pre-cleaning 101 Sample loading 102 Transfer 103 Final sample preparation 104 Chromatographic separation 105 Mass spectrometry (MS) detection 106 Spectrophotometric detection in the ultraviolet (UV) range 107 Post-cleaning

Claims

1. A device as a system (1) comprising modules (4, 22, 30) for the sampling, preconcentration and analysis of: - explosives in aqueous solutions and / or - UXO and munitions contamination in the sea and on the seabed, wherein the device as a system (1) comprises at least one housing (3) in which at least a first fluid system module (4) and / or a second fluid system module (30) and at least one analysis system module (22) are provided, with the following components in the first fluid system module (4): - at least three HPLC pumps (5, 14, 15), with different pumping capacities; - at least two valves (10, 11); - at least one sample selection valve (6), in the form of a 6-way valve with controllable setting options for waste and injection positions; - at least one in-line filter (13); with the following components in the second fluid system module (30): - at least one HPLC pump (36) and - at least one electronic control board (35) and with the following components in the analysis system module (22): - at least one mixer (23); - at least one valve (26), acting as a bypass valve; - at least one HPLC column heater (25); - at least one UV system (24) comprising a capillary waveguide and a spectral photometer; wherein - the first fluid system module (4) comprises - at least one syringe pump (16) with a 4-port distribution valve (17) and - the at least two valves (10, 11) have controllable transfer and loading / injection positions; - the analysis system module (22) comprises at least one ESI-MS (27); - the second fluid system module (30) comprises - a pressure housing (34); - a first pressure housing end cap A (31); - a second pressure housing end cap B (37); - at least one HPLC column selector (32), with at least two HPLC columns (33), as solid-phase extraction columns for sample collection; - in the presence of a second fluid system module (30), at least one of the pressure housing end caps (31, 37) comprises connecting elements which detachably connect the second fluid system module (30) to a respective analysis system module (22).

2. A method for sample collection, sample analysis and sample treatment using a device as a system (1) according to claim 1, comprising at least the following steps: a. Pre-purification (100) b. Loading of the sample (101) c. Transfer (102) d. Final sample preparation (103) e. chromatographic separation (104) f. mass spectrometry (MS) detection (105) g. spectrophotometric detection in the ultraviolet (UV) range (106) h. post-purification (107).

3. Method for sampling, sample analysis and sample treatment according to the preceding claim, wherein a respective subsequent sample or discrete sample from a sampling run is loaded onto the first solid-phase extraction column (9) simultaneously upon the arrival of a first sample in step c. Transfer (102).