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Chen Chao-jung - One of the best experts on this subject based on the ideXlab platform.
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The development of CE-MS and CEC-MS interfaces based on noncontinuous electrospray and chip-based microinjector
2007Co-Authors: Chen Chao-jungAbstract:利用非連續性電噴灑法，解決在無鞘流電泳質譜界面中所遭遇的電灑噴頭堵塞問題進而利用非連續性電噴灑的特性而發展出多通道低流速鞘流毛細管電泳質譜界面。另外，也利用短的毛細管電層析管柱銜接至晶片式微注射器以達到快速分析之目的。 在較靈敏的無鞘流毛細管電泳界面中，由於毛細管電泳的電滲流流速約為50~250 nL/min，電噴灑頭之口徑通常需被拉尖到~ 20 µm以下以符合理想噴灑流速。然而對於一個拉尖的噴頭而言，在塗佈導電層到噴頭時容易出現噴頭的損毀以及在分析進行時造成噴頭的堵塞。為了解決上述因為噴頭口經縮小所導致的問題，使用與分離管內徑ㄧ樣的噴頭口徑做電噴灑，再利用非連續性的電噴灑法以有效的增加噴灑流速到最佳流速。在20 Hz，20 %工作週期下可以得到較強且穩定的訊號。離子阱的最大離子進樣時間設定為10 ms，以避免離子儲存的平均效應。從實驗結果得知，使用50 µm口徑的噴灑頭時，在150 nL/min的操作流速下，非連續性電噴灑法可得到比連續性噴灑訊號更強且穩定的訊號。 為了有效提升毛細管電泳質譜的通量分析，開發出多通道低流速鞘流毛細管電泳質譜界面。由於低流速鞘流界面有較小的樣品稀釋比例且可產生較小的電噴灑液珠, 因此它有著比一般商業化電噴灑界面更靈敏以及更抗鹽的特性。然而由於低流速鞘流界面的噴灑流速較小，因此噴灑頭需很靠近質譜進樣端，使得原先在多通道毛細管界面中的金屬旋轉盤無法放置其中。為了使低流速鞘流界面可被應用在多通道毛細管電泳質譜，我們利用非連續電噴灑的概念，使此四根毛細管電泳產生序列式噴灑，再與質譜儀同步化。由於此四根樣品訊號可以不互相干擾並被分別呈現，因此成功的開發出多通道低流速鞘流毛細管電泳質譜界面。 為了使毛細管電層析質譜達到快速且自動化的分析，利用短的填充式毛細管電層析管柱銜接上晶片式微注射器以取代一般的整合式晶片毛細管電層析質譜。因為微注射器可產生較小的樣品帶寬，且可自動化，以及短管柱上的快速分析，因此，此裝置不僅可以保留微流體晶片分析的優點更可以避免在晶片內填充靜相顆粒的困難。 此外，也開發了晶片式微注射器的流體動力進樣方法，使其有著更穩定且快速的樣品進樣。在壓力進樣下，因為受限於填充式分離管柱的背壓，樣品只會流向進樣通道與樣品廢液通道，因此可以在晶片注射器上製備短的進樣通道以形成特定的進樣帶寬。並利用針筒式幫浦以及ㄧ個六向閥，使得樣品可在微注射器上做流動注入。如此，不僅可提供較穩定的注射方法，並可以針對大量樣品做快速注入分析，且已成功的應用在蛋白質水解片段上的序列分析。Several approaches based on noncontinuous spray and chip-based microinjector have been developed to overcome the clogging problem in sheathless CE-MS, and to increase the throughput in CE and CEC-MS. To develop a more practical and sensitive CE-MS interface, a sheathless pulsed–ESI interface has been developed for coupling capillary electrophoresis (CE) with ion trap mass spectrometer (MS). In sheathless CE-MS, because the EOF in CE is about 50~250 nL/min, in order to meet the optimal flow rate of the sprayer, the orifice of the sprayer has to be tapered down to ~20 µm or less o.d. Nevertheless, the susceptibility of breaking or clogging of the tip during coating or sample analysis limits the application of the tapered tips having small orifices. The use of noncontinuous spray mode allows the use of a sprayer with a larger orifice thus alleviate the problem of column clogging during conductive coating and CE analysis. A pulsed ESI source operated at 20 Hz and 20% duty cycle was found to produce the optimal signals. For better signals, the maximum ion injection time in the ion-trap mass spectrometer has to be set to a value close to the actual spraying time (10 ms). Using a sprayer with 50 µm o.d., more stable and enhanced signals were obtained in comparison with continuous CE-ESI-MS under the same flow rate (150 nL/min). The utility of this design is demonstrated with the analysis of synthetic drugs by capillary electrophoresis-mass spectrometry (CE-MS). For increase the throughput in CE-MS, a multiplex electrophoresis–mass spectrometry using four low flow sheath liquid ESI sprayers has been developed. Because of low sample dilution and the producing of smaller droplets, low flow interface is known to outperform conventional sheath liquid interface in sensitivity and the tolerance of salts. In a low flow interface, the sprayer is very close to the MS entrance for better ion transmission and because of the limited space between the sprayer and the entrance aperture of the ESI source, multiplex can not be achieved with the conventional rotating plate approaches. Based on noncontinuous spray for each sprayer, the multiplex low flow System was achieved by applying ESI potential sequentially to the four low flow sprayers, resulting in only one sprayer being sprayed at any given time. The synchronization of the scan event and the voltage relays was accomplished by using the data acquisition signal from the ion trap mass spectrometer. By synchronization, the ESI voltage was provided to the sprayers sequentially according to the corresponding scan event. With this design, a four-fold increase in analytical throughput was achieved. To perform fast analysis in CEC-MS approach, an approach to perform chip-based packed CEC-MS was proposed. This fast CEC-MS approach was based on a chip-based microinjector and a short fritless CEC column. Unlike integrated CEC chip, a chip-based poly-(dimethylsiloxane) (PDMS) microinjector was incorporated with a short fritless packed CEC column. By taking the advantages of small sample plug produced in channel cross intersection, automation in sample injection and separation, and fast separation because of a short CEC column, the proposed approach not only preserved the merits of chip analysis (fast separation and automation) but avoid the difficulty in packing ODS particles inside a chip. For better ESI sensitivity, this device was coupled with MS using a low flow sheath liquid interface. The potential and limitation of this device were evaluated in the analysis of a peptide mixture. To develop a more reliable sample loading method and to increase the throughput in sampling, a flow injection sampling method has been implemented for fast CEC-MS analysis. Because of the high back pressure of the CEC column, sample from the syringe pump will flow only into the sampling and waste channel. Therefore, a sample plug was formed according to the length of the sampling channel. With the incorporation of a six-port valve and a syringe pump to the chip microinjector, sample was delivered to the sampling channel at a flow rate of 1.56 µL/min. This simple and semi-automation System allows rapid sampling and high sample throughput. The potential and limitations were demonstrated in the analysis of peptides and protein digestion.Contents Chapter 1 Introduction…………………………………………….…….1 1.1 Introduction……………………….………………………………………..1 1.2 Capillary electrophoresis……………..…………………………………….3 1.2.1 Electrophoresis……………………….……………………………....4 1.2.2 Electroosmosis…………………………….………………………....5 1.2.3 Separation efficiency ………………………..………………….……7 1.2.4 Separation mode………………………………………………..……10 1.2.5 Capillary electrochromatography ……..……………………….........11 1.3 Electrospray………………………………………....………………..……13 1.3.1 Nano-electrospray ionization……………………….…………..……14 1.4 CE-MS interface………………………………………………..……….….17 1.4.1 Sheathless interface……………….……………………….…….….17 1.4.2 Sheath flow interface…………………………………………...…...18 1.4.3 Liquid junction interface…………….………………………..….….19 1.4.4 Low flow interface………………………….……………….…..…..20 1.5 CEC-MS interface………………………………………….……….…..…..21 1.6 Mass analyzer-quadrupole ion trap…………………………….…….…..…23 1.6.1 The three-dimensional quadrupole ion trap………………….….…....23 1.6.2 The two-dimensioanl quadrupole ion trap………………………….24 1.7 References …………………………………………………………….....25 Chapter 2 Sheathless capillary electrophoresis/mass spectrometry using a pulsed electrospray ionization source..…………………………………………45 2.1 Introduction………………………………………………………………45 2.2 Materials and methods……………………………………………….…..49 2.2.1 Reagents……………………………………………………………49 2.2.2 Preparation of the conductive rubber coated tapered capillary tip…49 2.2.3 Continuous ESI-MS and pulsed ESI-MS…………………………..50 2.2.4 The CE-pulsed ESI-MS…………………………………………….52 2.2.5 CE-continuous ESI-MS and CE-pulsed ESI-MS analysis of synthetic drugs………..………………………………….…….......52 2.3 Results and discussion……………………………………………….…...54 2.3.1 Voltage at pulse off…………………………………………….……54 2.3.2 Conductive rubber coating………………………………….………54 2.3.3 Duty cycle and pulse frequency in pulsed ESI…………….……….55 2.3.4 Effect of ion injection time in pulsed ESI………………….……….56 2.3.5 Pulsed ESI-MS versus continuous ESI-MS……………..…….…....58 2.3.6 CE-pulsed ESI-MS versus CE-continuous ESI-MS……….....….58 2.4 Conclusions………………………………………………………….…60 2.5 References………………………………………………………….…..61 Chapter 3 The development of multichannel capillary electrophoresis/mass spectrometry using low sheath flow interfaces…..………………………………81 3.1 Introduction…………………….………………………………………81 3.2 Materials and methods…………………………………………………84 3.2.1 Reagents…………………………………...……………………..84 3.2.2 The fabrication of a Low-Flow interface…………….…………….84 3.2.3 Multiplexed low flow ESI interface………………….…………..85 3.2.4 Multichannel CE-MS analysis……………………………….…...86 3.3 Results and discussion………………………………………………….88 3.3.1 Low flow interface…………………………………………….….88 3.3.2 Sequential spray…………………………………………………..88 3.3.3 The synchronization of the scan event and the voltage relays..…..89 3.3.4 ESI signals vs. sprayer position………………………….……….91 3.3.5 Intersprayer cross talk………………………………………….....91 3.3.6 Multiplexed low flow CE/MS System and cycle time……………92 3.4 Conclusions……………………………………………………………….95 3.5 References……………………………………………………………...…96 Chapter 4 A Chip-based Microinjector Incorprated to Fast CEC-MS…………………………………………..….....113 4.1 Introduction…………………………………………………………........113 4.2 Materials and methods………………………………………………........117 4.2.1 Chemicals………………………………………………….……......116 4.2.2 Preparation of a fritless packed CEC capillary column…….............118 4.2.3 The fabrication of Chip-based microinjector……………….………119 4.2.4 Incorporation of chip-based microinjector and a fritless CEC column………………………………………………………….…120 4.2.5 PMMA-based low flow interface…………………………………...121 4.2.6 Chip CEC-ESI/MS……………………………………………….…121 4.2.7 Mass spectrometer……………………………………………….….122 4.3 Results and discussion………………………………………………….…123 4.3.1 PDMS-based microinjector………………………………………….123 4.3.2 Incorporation of a PDMS microchip and a fritless CEC column……124 4.3.3 Fritless CEC column…………………………………………………125 4.3.4 PMMA-based Low flow interface……………………………….......126 4.3.5 Chip-based CEC-MS in the analysis of peptides………………….....128 4.4 Conclusions……………………………………………………………..….131 4.5 References…………………………………………………………….…....132 Chapter 5 Fast CEC-MS based on flow injection sampling and a chip microinjector incorporated with a short packed CEC column 5.1 Introduction………………………………………………………………….155 5.2 Materials and methods………………………………………………………159 5.2.1 Chemicals…………………………………………………...…………159 5.2.2 In-solution digestion…………………………………………………...160 5.2.3 Preparation of a fritless packed CEC capillary column………………..160 5.2.4 The fabrication of a microinjector……………………………………..160 5.2.5 PMMA-based low flow interface………………………………………162 5.2.6 Instrument setup………………………………………………………..162 5.2.7 Chip CEC-ESI/MS……………………………………………………..163 5.2.8 Mass spectrometer……………………………………………………...163 5.3 Results and discussion………………………………………………………..165 5.3.1 The design of the chip microinjector…………………………………...165 5.3.2 Incorporation of a chip microinjector with a capillary………….……...166 5.3.3 Direct sample injection…………………………………………………167 5.3.4 Loading time for flow injection sampling……………………………...168 5.3.5 Flow injection sampling………………………………………………...169 5.4 Conclusions……………………………………………………………………171 5.5 References……………………………………………………………………..172 Conclusions………………………………………………………………….....187 Figure contents Figure 1.1: Representation of the electrical double layer versus distance from the capillary wall…………………………………………………………..29 Figure 1.2: Representation of plug-like flow versus hydrodynamic flow……............30 Figure 1.3: Schematic representation of a packing CEC column with sintered frits…31 Figure 1.4: Schematic representation of Electrospary ionization (ESI)………………32 Figure 1.5: Flow rate profile for a 20 µm orifice sprayer. The ion count trace was obtained by monitoring the molecular ion of glufibrinopeptide on a quadruple mass spectrometer……………………………………….……...33 Figure 1.6: Flow profile for for sprayers of different inner diameters…………….….34 Figure 1.7: Schematic illustration of the CZE-MS using a sheathless ESI interface....35 Figure 1.8: Schematic illustration of the CZE-MS using a sheath flow ESI interface..36 Figure 1.9: Schematic illustration of CE-MS using a liquid junction ESI interface.....37 Figure 1.10: Schematic representations of the low flow sheath liquid ESI interface…38 Figure 1.11: Schematic of a sheathless CEC-MS interface. The sprayer was connected to the CEC column by a metal connector…………….….…..39 Figure 1.12: Representation of three-dimensional quadrupole ion trap mass spectrometer…………………………………………………..….……40 Figure 1.13: Schematic of a three-dimensional quadrupole ion trap analyzer…….…41. Figure 1.14: Schematic of a two-dimensional quadrupole ion trap mass spectrometer……………………………………………………………..42 Figure 1.15: Schematic representation of a two-dimensional quadrupole ion trap analyzer…………………………………………………………………43 Figure 1.16: Ions were ejected through the two slots and detected by the two outer detector Systems………………………………………..………………...44 Figure 2.1: Series of frames with second labeled in one cycle of pulsed ESI (0.8 Hz)…………………………………………………………………...64 Figure 2.2: Photograph of the pulsed nanoelectrospray source……………………….65 Figure 2.3: Schematic representation of the pulsed voltage generator by a digital function generator and a voltage-multiplied circuit……………..66 Figure 2.4: The display of pulsed voltage peaks on an oscilloscope. The pulsed generator consisted of a digital function generator and a voltage-multiplied circuit……….………………………………….……...67 Figure 2.5: Photograph of the pulsed voltage generator which consisted of a relay card and a high voltage relay………………………………….……68 Figure 2.6: LabVIEW System for pulsed ESI interface……………………………….69 Figure 2.7: Schematic representation of the CE-pulsed ESI-MS setup……………….70 Figure 2.8: (a) Photograph of a 50 µm orifice sprayer coated with conductive rubber. (b) The total ion current (TIC) of 1 ppm reserpine…………………….….71 Figure 2.9: Schematic representation of the pulsed spray. The eluent is accumulated at 1kV and sprayed out at 2 kV…………………………72 Figure 2.10: The display of pulsed voltage peaks on an oscilloscope. The pulsed voltage generator consisted of a relay card and a high voltage relay…..73 Figure 2.11: The TIC of 1 ppm rserpine. The sample was injected by infusion. The pulsed spray was operated at 10 Hz, 20% duty cycle and 20 Hz, 20% duty cycle, respectively………………………………….74 Figure 2.12: (a) The TIC of reserpine at different maximum injection time in pulsed ESI. The MH+ ion of reserpine at (b) 10 ms injection time and (c) 200 ms injection time………………….…………………….75 Figure 2.13: Schematic representation of “averaging effect” on the maximum ion injection time setting…………………………………….………..76 Figure 2.14: The TIC of 1ppm reserpine (a) using a pulsed ESI at 150 nL/min and (b) using a continuous ESI at 150, 300, 500,700, and 1000 nL/min flow rate. (c) The MH+ ion of reserpine obtained from pulsed spray at 150 nL/min flow rate. (d) The MH+ ion of reserpine obtained from continuous spray at 150 nL/min flow rate…………………..…..77 Figure 2.15a: Mass electropherograms of a 60 ppm synthetic drug mixture using pulsed ESI in positive ion mode. The pulsed ESI was set at 20 Hz frequency and 20% duty cycle……………………….………………..78 Figure 2.15b: Mass electropherograms of a 60 ppm synthetic drug mixture using continuous ESI in positive ion mode……………………….…79 Figure 3.1: Schematic representation of the multiplexed sheath flow CE-MS interface………………………………………………………………….98 Figure 3.2: Schematic representations of the low flow sheath liquid ESI interface…99 Figure 3.3: Scan event settings on the data dependent System……………………....100 Figure 3.4: Structures of the eight synthetic drugs……………………….…………101 Figure 3.5: Photograph of the multiplexed low flow ESI interface………..……..…102 Figure 3.6: Schematic representation of the multichannel CE/MS using four low flow sheath liquid interfaces…………………………………..…..103 Figure 3.7: The LabVIEW program for low flow multiplexed CE-MS……..……..104 Figure 3.8: The display of the 5 volt pulsed signals. The signals were acquired from DRQ 1 and modified by labVIEW to produce a 5 volt in strength……………………………………………..…….…..105 Figure 3.9: The synchronization between spray and scan events……………..……106 Figure 3.10: Photograph of the multiplexed CE/low flow ESI interface mounted on a PMMA stand in front of the sampling cone of LCQ…..107 Figure 3.11: Mass spectrum of 100 ppm predisolone from individual sprayer…..…108. Figure 3.12: Crosstalk of the four-channel multiplex CE/MS System. Extracted ion electropherograms from four columns. 500 ppm acetaminophen (m/z 152)……………………………………………109 Figure 3.13: Crosstalk of the four-channel multiplex CE/MS System. Extracted ion electropherograms from four columns. 1000 ppm acetaminophen (m/z 152)……………………………………………110 Figure 3.14: Currents flowing in a simple CE/MS System using a CE high-voltage supply and an ESI high-voltage supply……………...111 Figure 3.15: Multi-CE /low flow ESI-MS analysis of four mixtures. Extracted ion electropherograms of the eight synthetic drugs……..112 Figure 4.1: Chip layout for fritless CEC in poly(dimethylsiloxane) (PDMS). The separation column includes a gradual tapering just below the intersection, which is used to stop stationary-phase particles, leaving the injector particle-free……………………………………136 Figure 4.2: Diagram of the “keystone effect”. These first particles act as the “keystones”, blocking the others and allowing the packed segment to grow longer in the opposite direction…………………..137 Figure 4.3: (a) Schematic drawing of CEC chip layout, showing channel widths, and numbering scheme for reservoirs. (b)Photomicrograph of column packed with 1.5 µm diameter ODS beads. (c) Drawing of cross-section of packed chamber, showing weir heights (9 µm) in relation to channel depth(10µm) and particle size(1.5 ~ 4µm)…....138 Figure 4.4: (a) Schematic of the PDMS microchip used for CEC and preconcentration. Reservoirs: 1, sample; 2, buffer; 3, sample waste; 4, bead introduction; 5, waste. (b) Expanded view of a bead chamber. (c) Detailed structures of inlet and outlet frits………....…139 Figure 4.5: (a) Schematic diagram of the microchip integrated CEC System. (b) Microchip ESI interface……………………………………………..140 Figure 4.6: Photograph of the packing device. A 1.5-mL bottle filled with slurry of packing materials was placed inside the pressure vessel...…141 Figure 4.7: (a) Schematic design of the PMMA mold for microinjector. (b) Photograph of PDMS-based microinjector. A, B, C and D could be acted as buffer reservoirs………………………………….142 Figure 4.8: Schematic diagram of the wire-assisted epoxy fixing method. A 30µm diameter was inserted into the channel in the microinjector followed by an insertion into a fritless CEC column….143 Figure 4.9: (a) Schematic of a low flow interface for chip-based CEC-MS approach. (b) Photograph of the chip-based CEC-MS coupled with a low flow ESI interface……………………………………………...144 Figure 4.10: Voltage applied in (a) floating mode and (b) direct injection mode...145 Figure 4.11: LabVIEW software for voltage control in chip-based CEC-MS……146 Figure 4.12: Photograph of the chip-based CEC-MS device mounted on the x-y-z translation stage in front of the sampling cone of LTQ…..147 Figure 4.13: A photomicrograph of a 50 µm i.d. channel of a PMMA chip after flushing with 30% ACN for (a) 1 min. and (b) 13 min……………...148 Figure 4.14: Schematic representation of the Low-Flow sheath liquid CEC/ESI-MS interface………………..……………………………..149 Figure 4.15: Mass electrochromatograms of a five-peptides mixture (4 µM). Floating injection mode………………………………………….…..150 Figure 4.16: Mass electrochromatograms of a five-peptides mixture (4 µM). Direct injection mode………………………………………………..151 Figure 4.17: Mass electrochromatograms of a five-peptide mixture by a 30 cm column CEC-MS approach………………….……………..152 Figure 5.1: (a) Schematic view of the mechanical actuation of the PDMS membrane on the sample reservoir for pressure pulse injection. (b) CE chip is designed for pressure injection and is composed of microchannels etched on two slides…………………………………..174 Figure 5.2: Schematic diagram of a two-way micro-8-port valve connected to a micro-channel network……………………………………………….175 Figure 5.3: Instrumental schematic representation of flow injection sampling for capillary-based CE System……………………………………………176 Figure 5.4: (a) Schematic diagram of flow-through sampling for the microchip System. (b) Voltage gating scheme for sample injection using flow-through injection method……………………………………….177 Figure 5.5: (a) Schematic design of the PMMA mold for chip microinjector used for flow injection sampling. (b) Photograph of a PDMS-based microinjector with a short sampling channel…………………………178 Figure 5.6: Schematic diagram of the flow-injection sampling for the microinjector-short CEC column device………………………...……179 Figure 5.7: Schematic diagram of the sample plug formed in the sampling channel after applying the separation voltages………………………………..180 Figure 5.8: Mass electrochromatograms of four peptides (10 µM) by direct injection using a pump. Sampling time: 400 nL/min for (a) 3s (b) 60s (c) 90s………………………………………………………….181 Figure 5.9: Effect of the sampling channel length on the peak width of angiotensin II………………………………………………………..…182 Figure 5.10: Sample profile in the sample delivering capillary based on the flow injection sampling method…………………………………………...183 Figure 5.11: Fast CEC-MS analysis by flow injection sampling of angiotensin II...184 Figure 5.12: Mass electrochromatograms of a mixture of peptides (10 µM) by flow injection sampling…………………………………………..185 Figure 5.13: The base peak electrochromatogram of tryptic perptides from albumin (bovine serum) (50 µM) by flow injection sampling……….186 Table contents Table 4.1: Comparison of resolution between chip-based CEC-MS and long column CEC-MS approach in the analysis of a five-peptide mixture…..15
V M Leon - One of the best experts on this subject based on the ideXlab platform.
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input of pharmaceuticals through coastal surface watercourses into a mediterranean lagoon mar menor se spain sources and seasonal variations
Science of The Total Environment, 2014Co-Authors: R Morenogonzalez, Sara Rodriguezmozaz, Meritxell Gros, E Perezcanovas, Damia Barcelo, V M LeonAbstract:The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujon watercourse to the Mar Menor lagoon were determined by UPLC–MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, β-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L− 1 for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow System, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujon watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%).
R Morenogonzalez - One of the best experts on this subject based on the ideXlab platform.
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input of pharmaceuticals through coastal surface watercourses into a mediterranean lagoon mar menor se spain sources and seasonal variations
Science of The Total Environment, 2014Co-Authors: R Morenogonzalez, Sara Rodriguezmozaz, Meritxell Gros, E Perezcanovas, Damia Barcelo, V M LeonAbstract:The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujon watercourse to the Mar Menor lagoon were determined by UPLC–MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, β-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L− 1 for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow System, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujon watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%).
Sara Rodriguezmozaz - One of the best experts on this subject based on the ideXlab platform.
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input of pharmaceuticals through coastal surface watercourses into a mediterranean lagoon mar menor se spain sources and seasonal variations
Science of The Total Environment, 2014Co-Authors: R Morenogonzalez, Sara Rodriguezmozaz, Meritxell Gros, E Perezcanovas, Damia Barcelo, V M LeonAbstract:The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujon watercourse to the Mar Menor lagoon were determined by UPLC–MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, β-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L− 1 for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow System, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujon watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%).
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input of pharmaceuticals through coastal surface watercourses into a mediterranean lagoon mar menor se spain sources and seasonal variations
Science of The Total Environment, 2014Co-Authors: R Morenogonzalez, Sara Rodriguezmozaz, Meritxell Gros, E Perezcanovas, Damia Barcelo, V M LeonAbstract:The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujon watercourse to the Mar Menor lagoon were determined by UPLC–MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, β-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L− 1 for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow System, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujon watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%).
