Polychlorinated biphenyl is an organic industrial chemical whose find and use is traced to hold been since 1929. It has a Chemical Abstract Service figure Aroclor 1242, CAS No: 53469-21-9. Its H2O solubility is 0.01-0.0001 I?g/L at 25A°C, octanol-water divider coefficient of 4.3-8.26 and vapour force per unit area of 1.6-0.003 ten 10-6 millimeter Hg at 20A°C ( UNEP, 2002 ) . These physic-chemical belongingss confer on it the possible for atmospheric long scope conveyance, long half-life therefore doing it characteristically relentless and toxic. It was used as heat exchange fluid, as transformer and capacitance oil, pigment additives and plastics. Though its production and use was banned in 1979 ( USEPA, 2012 ) it is still found in the environment and most amazingly in pristine locations such as the Arctic.
In puting out for a field research such as the Arctic, the experimental design and protocol is mostly determined by the aim of the research, such as monitoring, tendency sensing etc. The cardinal inquiries that are needed prior to trying are encapsulated in the sampling and analysis program which addresses the informations quality aim ( Zhang, 2007 ) .
The climatic status of the north-polar makes it preponderantly icy and snowy. Because of the variableness of in its physical province ; assortment of methods exists for H2O sampling in the Arctic Ocean. This could be achieved by trying snow, ice or dissolved H2O. In H2O, snow and air sampling, a cardinal factor that has to be taken into consideration includes, the representativeness of samples to be collected, besides for air sample aggregation should be done giving consideration to meteoric and topographic factors.
Snow has been demonstrated to be a good scavenger for semi-volatile organic compounds and relentless organic pollutants such as PCBs ( Wania et al. , 1999 ) . The snow surface country bing with standing snow battalion or falling snow tends to command the measure of chemical sorbed and besides heterogenous reactions for compound that are rather reactive ( Sumner and Shepson, 1999 ) . This implies that snow could move as a impermanent storage for contaminations.
Organic contaminations in the north-polar are normally low, so there is demand to try high volumes that will be representative of the environment and besides enable contaminations to be detected ( Franz and Eisenreich, 1998 ) . In snow sampling, different sampling stations have been used such as Teflon-bags, metal case shots, low denseness polythene bottles ( LDPE ) , Snow-cans and snow-tubes. Other stuffs needed include baseball mitts, steel shovels and particular trying outfits.
An air tight 50L snow-can or a 7.5L snow-tube can be employed. These sampling stations are alone because they are sealed after sample aggregation and allows for the analysis of caput infinite ( Herbert et al. 2004 ) . The 50L allows for trying of low denseness snow and every bit creates room for higher snow volume that is required to obtain adequate melt-water needed to accomplish measureable concentrations. Besides, it permits snow sample to be split into headspace, melt H2O and particulate affair. An upper and lower pat for the palpebra and base of the snow-can allows for emptying of headspace and drainage of melt-water severally. The snow tubing allows for trying higher denseness snow and for aggregation of snow from defined beds due to its narrow diameter ( Herbert et al. 2004 ) .
Figure I: Specially designed 50L snow trying can and 7.5L snow trying tubing for Arctic field work.
Adapted from Herbert et Al. 2004
Before puting out for trying, the snow-can, tubing and shovel should be decontaminated by rinsing with propanone, methylene chloride and hexane and kept in adust aluminum foil until trying ( Quiroz et al. , 2008 ) . Trip or travel spaces are prepared prior to go forthing for the field and maintain together with sample containers. The ground for this is to measure mistake associated with transportation and handling. At the field, the operator should be good kitted in field garb inclusive of baseball mitts. Sampling is conducted several metres off from the snow vehicle ( 100m ) commendation and from weather side. Prior to snow aggregation, equipment space or rinsate spaces are taken by utilizing the pre-cleaned equipment to roll up and make full the appropriate container with analyte free H2O. Snow spaces are to be prepared by rinsing a pre-cleaned sampling station in the field with 250 milliliters Milli-Q H2O and later extracted and treated like a snow meltwater. Snow samples are so collected utilizing the shovel and transferred to the snow-can and spiked with a foster recovery criterion incorporating PCB congeners before sealing off the container. Field replicate samples are besides collected to find trying preciseness, assess intrinsic sample variableness and trying point representativeness ( Popek, 2003 ) . As portion of quality control step, field spaces are prepared in the field and undergoes at the same time full handling and transporting procedure of an existent sample. It is aimed at observing sample taint that can happen during field operation or cargo. ( Zhang, 2007 ) .
In the research lab, samples are treated in batches. Snow samples are allowed to run at room temperature ; the caput infinite is purged through a glass cartridge and evacuated with a vacuity pump ( Herbert et al. 2004 ) . Solid stage extraction of melt-water is carried out for about 12 hours. Interventions from H2O are removed by eluting with methyl alcohols, while the analytes are eluted with hexane and methylene chloride. The solvent fractions are collected, soxhlet extracted for 16hrs, evaporated and eventually reduced in watercourse of N. The analyte are passed through alumina-silica and gel pervasion chromatographic clean up procedures and farther reduced in a watercourse of N. After which it is transferred into dodecane ( 25 ul ) with the add-on of PCB internal criterions and fixed for measuring utilizing the gas chromatography-mass spectroscopy. Afterwards, the per centum recoveries should be calculated for both recovery and internal criterions to look into if they are within acceptable scope and subsequent rectification or standardization made.
QUALITY CONTROL PROTOCOLS.
A scope of quality control measures incorporated both in the field and research lab to look into for mistakes that could originate in the analytical procedures includes.
Travel or trip spaces are normally designed for trying events affecting volatile organic compounds ( VOCs ) . It is prepared prior to field work and maintain closed, transported to the field and back to the research lab the same manner other samples are handled. Its usage is to measure mistakes that may originate from transporting, managing and analytical processs.
Field spaces samples are prepared in the field for sensing of sample taint that could originate during field operation and cargo.
The alternates or a recovery spike is an organic compound similar to the analyte of involvement added to the analytical sample during sample readying. It is spiked in all spaces and samples and used to measure per centum recovery and public presentation method.
Reagent spaces are employed to observe contaminations that may be introduced into the sample during readying and analysis. It is normally analyte-free H2O analysed with the samples of involvement.
Instrument spaces is a clean sample such as distilled H2O or another dissolver injected and processed through the measurement instrument to find instrument taint or carry over sample. This done during the gas chromatography mass spectroscopy measuring.
The matrix spike and it is aimed at finding the consequence of matrix on analyte recovery. The samples are spiked with known sum of analyte and subjected to all preparatory and analytical processs.
Lab extras are besides incorporated as a quality control step during analysis to observe hapless analytical duplicability or hapless homogenisation in the field. This is an aliquot of the same sample that are prepared and analysed at the same clip but normally submitted and analysed as separate samples.
Calibration criterions are standard solutions used to obtain standardization curves. The standard solutions frequently range from lower to higher concentrations.
Internal criterions are chemically similar to the analyte but are non expected to be present in the sample and should non besides interfere in the analysis. The ground for utilizing this is to polish the standardization procedure and compare analytical signals for standardization to those of internal criterion ( Popek, 2003 ; Zhang, 2007 ) .
This whole scope of scope of quality control steps are aimed at geting at robust and persuadable consequences ( informations ) .
To accomplish a high quality and robust consequence, an ultra-clean room is designed in the sampling vehicle ( ship ) for hive awaying of samples until reaching to the research lab. The ultra-clean room is designed to forestall any background taint originating from the ship. The ship is anchored within an ice floe and engine switched off. Particular field dress is worn so as to forestall taint. Both ice blocks and ice nucleuss are to be collected utilizing unstained steel ice-core drills which have no lubricated portion and operated on electricity to forestall taint. The concatenation of the drill is to be exhaustively washed and solvent rinsed. Ice samples are collected several metres off from the ship and transferred into dual big volume chromium steel steel ice melters of approximately 370L each so as to obtain adequate samples that will enable sensing of the organic compound ( PCB ) . The transportation of samples into the melter should be rapid so as to cut down exposure clip. The two ice melters should be labelled in order to maintain path of cross taint between subsequent ice samples ( Gustafsson et al. , 2005 ) .
Figure 2: Specially designed large-volume ice-melting equipment developed for dedicated ultra-clean sampling and handling of hint organic substances from Arctic ice.
Life-size image ( 68 K )
Adapted from Gustafsson et al. , 2005
Use is made of polyurethane froth ( PUF ) which should be cleaned exhaustively anterior to field expedition to minimise space. The cleansing procedure is achieved by rinsing with detergent for 1hr at 90oC ( Sobek and Gustafsson, 2004 ) and drying at 50oC for 24hrs followed by soxhlet extraction in methylbenzene for 24hrs and propanone for 24hrs. Then it ‘s eventually dried in desiccator with a PUF scrubber at the gas jet or recess. Glass-fibre filters ( GFF ) or borosilicate filters are to be cleaned by baking at 450oC for 12hrs in a muffle furnace so removed, wrapped in aluminum foil that has been baked at 450oC and stored at -18oC until use. Large volume of saltwater ( 1000L ) should be collected so as to transcend the method sensing bound ( PCB concentration in the Arctic is expected to be really low ) . This is achieved utilizing a chromium steel steel pipe at deepness of 8m through the ship ‘s consumption system located in the keel or bow and straight deposited in the ultra-clean room designed for the expedition. The flow rate should be monitored and taken note of while the force per unit area over the GFF ( invariably monitored utilizing a force per unit area index so that it does non transcend 1bar in order to cut down cell lyzing ( Sobek and Gustafsson, 2004 ) . The pre-combusted fiber filter is used in aggregation of particle-associated PCBs and later through polyurethane froth adsorbents or XAD cartridge to roll up dissolved chemical of involvement ( PCBs ) . Collected samples are kept in adust aluminum foil envelopes and stored in plastic bags that is dual certain and kept in deep-freeze at a temperature of ( -18 to -20oC ) until analysis.
Apart from the quality control step mentioned in the sampling procedure, some other steps taken include ;
Parallel samples of the saltwater could be taken with a Kiel in situ pump and analysed otherwise as a complementary quality control step.
Field spaces and laboratory spaces are to be analysed in analogue with chief samples to function as control for anyA taint originating from the described sampling and analytical procedures.
Analytic spaces ( procedural spaces ) of PUF and GFF filters are to be arranged for and analysed during sample analysis.
A 2nd filter should be placed behind the chief filter and a separate analysis done to measure filter discovery and dissolved PCBs soaking up to the filter surface.
For the ice and H2O samples, 13C12-labeled PCB congeners should be added as internal criterions to each prior to soxhlet extraction with methylbenzene which is operated for 24-hrs. The samples are to be cleaned up by eluting in unfastened silicon oxide column and farther cleaned up through HPLC separation on a column of amino acid. After the everyday clean up processs, samples are to measured utilizing GC-MS operated in the negatron impact manner. Added to the sample is 13C12-labeled recovery criterion ( PCB congener ) before injection on the GC-MS for measuring. The internal and recovery criterion are added as quality control measures to look into for mistakes that may originate from the analytical procedure. The recoveries are to be calculated and possible corrections made for both recoveries and spaces for each of the samples.
Air sampling could be carried out utilizing high volume air sampling stations with polyurethane froth stoppers ( PUFs ) and glass fiber filter ( GFF ) as trying media. The polyurethane froth stoppers ( PUFs ) should be pre-extracted for 16hrs in methylene chloride ( DCM ) and dried in a desiccator while the GFF are pre-combusted at 450oC in the furnace before deployment ( Hung et al. , 2010 ) . Field and travel spaces are to be provided consisting of three or more pre-cleaned PUFs which is to be exposed to the ambiance all through the sampling period. The lower PUFs are to be tested for any possible discovery. Sampling stations are to be controlled by the usage of air current detector to guarantee samples collected are fluxing from the way of the ship ‘s bow in order to avoid sample taint from air stack emanations originating from the ship. Air samples of ( 1200 m3A air volume for 24hrs or hebdomadal which amounts to aspiration of 11,400 m3A of air. ) are absorbed on board utilizing the high volume air sampling station in forepart of the upper deck of the ship ( 20m above sea degree ) . The GFF traps the airborne atom while the PUF column traps the gaseous stage. Both the filters and air column are stored at -20oC until analysis ( Cai at al. , 2012 ) .
The PUF stoppers are to be pre-extracted with methylene chloride ( DCM ) while the GFF is to be pre-combusted at 450oC. Samples are to be spiked with a recovery criterion of 13C12 -labelled PCB congeners. Samples are to be soxhlet extracted and the infusion concentrated in a rotary evaporator and farther reduced in a watercourse of H. The infusion is to be cleaned up through aluminum oxide silicon oxide chromatography and gel pervasion chromatography. The resulting dissolver is to be exchanged with 25mL of dodecane incorporating PCB congeners as internal criterions. Instruments spaces should be taken and samples can be analysed by GC-MS operated at selected ion manner ( SIM ) .
QUALITY CONTROL AND ASSURANCE
Air columns should be pre-cleaned with organic dissolvers such as propanone, hexane and methyl alcohol.
The GFFs should be baked at 450oC for 12hrs prior to utilize while the PUF should be soxhlet extracted in hexane: propanone or methylene chloride.
Air columns should be given protection against UV- sunshine during trying by usage of aluminum foil in order to avoid debasement of mark compounds.
Field spaces and laboratory spaces dwelling of pre-extracted PUF should be at the same time engaged during trying and analysed during sample extraction and analysis.
The GFFs and the PUFs are to be analysed for all samples in order to cipher for any discovery of the analytes during sampling.
Passive air sampling stations should be kept in different parts of the ship and subsequently analysed so as to set up if taint was originating from the ship.
Field spaces should be used to cipher the method sensing bounds ( MDLs ) as 3times the standard divergence of the clean concentration.
Calibration criterions should routinely processed with each batch of samples.
Extremums should be integrated when the signal to resound ratio is high.
Instruments public presentation should be checked utilizing quality control criterions after each batch analysed.
There should be an analysis of mention stuff.
Figure: 3 High Volume Air Sampler.
hypertext transfer protocol: //www.learsiegler.com.au/images/uploads/Hi_Vol.JPG
Adapted from Lear Siegler Australasia ( hypertext transfer protocol: //www.learsiegler.com.au )
Figure: 4 Passive air trying device
Adapted from Gevao et al.,2006.
AIR MASS BACK-TRAJECTORIES
The wind way during the sampling period should be determined by analyzing meteoric informations. Individual air mom beginnings of samples collected during the sail sections should be calculated utilizing NOAA ‘s HYSPLIT theoretical account. Different meteoric informations ( e.g. , air temperature, wind way, wind velocity, visibleness, and atmospheric force per unit area ) should be measured and recorded.
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