1 00:00:45,640 --> 00:00:50,890 And dissolving it into tetrahydrofuran so this is a complete dissolution the 2 00:00:50,890 --> 00:00:58,600 plastic will dissolve and we now have a solution if you Sonic eight this sample 3 00:00:58,600 --> 00:01:05,470 while the when you first put the PVC toy in typically with the 1530 minute 4 00:01:05,470 --> 00:01:07,540 sonication you'll have a completely dissolve 5 00:01:07,540 --> 00:01:11,380 solution so it makes things a little bit quicker after we have a dissolve 6 00:01:11,380 --> 00:01:16,390 solution will precipitate in hexanes this removes a PVC from the solution so 7 00:01:16,390 --> 00:01:20,920 we'll get a solid precipitate that leaves a phalates in solution makes it a 8 00:01:20,920 --> 00:01:25,290 little bit easier to analyze so we'll move into the analysis step with GCMs 9 00:01:25,290 --> 00:01:30,790 and I'll mention here that the cpsc method allows for several alternative 10 00:01:30,790 --> 00:01:35,979 methods within it this is too important for testing labs of labs already 11 00:01:35,979 --> 00:01:40,630 familiar or likes to use a certain test method that method those that are listed 12 00:01:40,630 --> 00:01:45,720 are available to use instead so generally the alternative methods 13 00:01:45,720 --> 00:01:50,500 usually what differs is the extraction technique and most of them fall into one 14 00:01:50,500 --> 00:01:54,670 of the categories I have listed here a couple of them fall into just a typical 15 00:01:54,670 --> 00:01:59,500 fluid extraction where you're cutting up the sample and you're putting it into a 16 00:01:59,500 --> 00:02:05,619 solvent usually dichloromethane and letting it sit the California Department 17 00:02:05,619 --> 00:02:12,880 of toxic substances method asked just for a 15 minute time and the Health 18 00:02:12,880 --> 00:02:18,340 Canada method is much longer rate 12-hour time so even with this with this 19 00:02:18,340 --> 00:02:24,090 step you have a long range of sample times Sox flu extractions a more of a 20 00:02:24,090 --> 00:02:28,690 aggressive fluid extraction here you have an apparatus that I have shown on 21 00:02:28,690 --> 00:02:34,750 the right where your you have a ground-up sample and the solvent is is 22 00:02:34,750 --> 00:02:38,680 heated and then cool the solvent will come down through the sample so you're 23 00:02:38,680 --> 00:02:43,570 having a continuous extraction with fresh solvent usually the the methods 24 00:02:43,570 --> 00:02:48,280 call for about six hours methods under this category are the the Chinese method 25 00:02:48,280 --> 00:02:52,810 and European methods which I have listed and also EPA methods there's some other 26 00:02:52,810 --> 00:02:57,250 older methods that we we see using this as well there are a couple other 27 00:02:57,250 --> 00:03:00,690 techniques typically found with within the EPA 28 00:03:00,690 --> 00:03:07,080 methodologies they were looking at using different tools for your extraction such 29 00:03:07,080 --> 00:03:13,860 as using a microwave pressurized fluid extraction or ultrasonic extraction and 30 00:03:13,860 --> 00:03:20,010 the common bond here we're looking for is an analysis by GCMs we think this is 31 00:03:20,010 --> 00:03:24,300 important g CMS's are our preferred analysis technique because it's 32 00:03:24,300 --> 00:03:31,140 qualitative and quantitative here I have a chromatogram shown of an analysis with 33 00:03:31,140 --> 00:03:37,670 a standard of all six of the specifically regulated phalates and 34 00:03:37,670 --> 00:03:43,019 generally we're getting a pretty good separation especially for the lower 35 00:03:43,019 --> 00:03:50,670 molecular weight ones and obviously the dno PDI NP + di DP which you see in the 36 00:03:50,670 --> 00:03:56,010 later half the chromatogram alone around 11 12 minutes that's where things get a 37 00:03:56,010 --> 00:04:00,000 little bit trickier and we'll be talking a little bit more about that today we 38 00:04:00,000 --> 00:04:06,780 specified GCMs because some older methods call for GCF ID and simply put 39 00:04:06,780 --> 00:04:09,810 if you're having any overlap and you're chromatogram with different with 40 00:04:09,810 --> 00:04:14,670 different phalates f ID is just not strong enough to get a full qualitative 41 00:04:14,670 --> 00:04:21,840 and quantitative assessment so I'm gonna briefly go over some common problems I'm 42 00:04:21,840 --> 00:04:25,770 gonna give you very very simple problems and very simple solutions that probably 43 00:04:25,770 --> 00:04:31,260 don't do these justice but just to get a the the ideas flowing for discussion 44 00:04:31,260 --> 00:04:38,100 later some common questions we get often people are asked is there a standard 45 00:04:38,100 --> 00:04:45,810 reference material for phalates in PVC another common problem is false positive 46 00:04:45,810 --> 00:04:51,990 results many of manufacturers someone else might say I did not put phalates in 47 00:04:51,990 --> 00:04:56,160 this item I'm sure there's no phalates in this item but the test lab still said 48 00:04:56,160 --> 00:05:01,979 that that there are phalates in this so that could either come under a false 49 00:05:01,979 --> 00:05:07,370 positive result or a result of contamination somewhere along the lines 50 00:05:07,370 --> 00:05:11,910 another issue is the identity of dice and Nona land dice adecco Fowley 51 00:05:11,910 --> 00:05:17,340 both of these phalates actually have multiple cast numbers so there's 52 00:05:17,340 --> 00:05:22,080 different ways of making these compounds and there's a different chemical formula 53 00:05:22,080 --> 00:05:29,100 of these compounds so try it to trying to summarize some of these issues and 54 00:05:29,100 --> 00:05:36,330 solutions as best we can there are multiple issues of the cpsc 55 00:05:36,330 --> 00:05:40,710 method it's been updated a few times we're now on the third version sometimes 56 00:05:40,710 --> 00:05:45,720 people with problems they'll contact us and say well I was following the first 57 00:05:45,720 --> 00:05:50,190 version of this and this is a problem I've had there are there are significant 58 00:05:50,190 --> 00:05:54,150 advancements between the versions so make sure you're definitely using the 59 00:05:54,150 --> 00:06:01,020 most current one we have an interagency agreement with NIST to develop standard 60 00:06:01,020 --> 00:06:06,690 reference materials this has been an ongoing project the last update has been 61 00:06:06,690 --> 00:06:11,370 that they're hoping to have something within the next calendar year we'll see 62 00:06:11,370 --> 00:06:17,970 how that develops but this is a promising idea there's also some 63 00:06:17,970 --> 00:06:21,680 companies that we've seen I believe specs Serta prep has started issuing a 64 00:06:21,680 --> 00:06:27,890 certified reference material they have a specific level of phalates in 65 00:06:27,890 --> 00:06:32,580 polyethylene so that's another frontier you can look with standards companies 66 00:06:32,580 --> 00:06:36,720 they may also be developing their own or looking for something along those lines 67 00:06:36,720 --> 00:06:43,170 I mentioned contamination before this is possible and this is a good question to 68 00:06:43,170 --> 00:06:48,360 ask if you're a manufacturer or seller essentially from the starting points at 69 00:06:48,360 --> 00:06:51,960 the endpoint have I looked at every possible area where phalates can come 70 00:06:51,960 --> 00:06:57,690 into my line we've heard of recycling plastics sometimes people use recycled 71 00:06:57,690 --> 00:07:02,040 plastics that had fights and before and that could that level of phalates and 72 00:07:02,040 --> 00:07:09,270 the new material could be enough to lead to a failure also is the equipment 73 00:07:09,270 --> 00:07:12,210 that's being used and they've run phalates and they've been properly 74 00:07:12,210 --> 00:07:18,090 cleaned essentially you need to break down and look at every step are you sure 75 00:07:18,090 --> 00:07:23,610 that every step of the way is there's no way that contamination can come in to 76 00:07:23,610 --> 00:07:29,180 this issue and finally a lot of our suggestions and 77 00:07:29,180 --> 00:07:33,980 emphasis is on qualitative analysis by technical staff and I'll be going into 78 00:07:33,980 --> 00:07:41,300 this more but we have a few key points here we are CPSC method calls for a 79 00:07:41,300 --> 00:07:45,050 retention time match with a standard phalates so make sure when you're 80 00:07:45,050 --> 00:07:48,470 looking at the chromatogram and the chromatogram of a sample a retention 81 00:07:48,470 --> 00:07:53,510 time must match or else that should be a red flag also a mass spectrum match this 82 00:07:53,510 --> 00:07:57,710 and not just a general mass spectrum but the iron ratio is very important and can 83 00:07:57,710 --> 00:08:03,710 help in identifying blank analysis is crucial for looking for contamination 84 00:08:03,710 --> 00:08:08,030 within the lab result itself if you run a blank and you're seeing phalates in 85 00:08:08,030 --> 00:08:13,100 there that means you have contamination along somewhere along the line if people 86 00:08:13,100 --> 00:08:18,710 are reusing glassware we found in our lab that our GCMs Inlet liner sometimes 87 00:08:18,710 --> 00:08:23,960 can carry these fat lights over so it's they're persistent enough that they can 88 00:08:23,960 --> 00:08:30,020 come along the line even within the lab and I mentioned before the ein P and D 89 00:08:30,020 --> 00:08:35,360 IDP have multiple caste numbers if you look closely new and you get standards 90 00:08:35,360 --> 00:08:39,590 of both you'll see there chromatogram peak shape is a little different so this 91 00:08:39,590 --> 00:08:43,850 is a great way to identify which material you're working for and you 92 00:08:43,850 --> 00:08:49,520 should be if you're quantifying one specific caste number of di MP or di DP 93 00:08:49,520 --> 00:08:55,580 your standard should be that same caste number so you get a fully well developed 94 00:08:55,580 --> 00:09:01,580 match so I'll just give you a few examples of why a strong qualitative 95 00:09:01,580 --> 00:09:07,040 assessment I'll help here I have two chromatograms one is of di NP and the 96 00:09:07,040 --> 00:09:12,260 other is of a common Fallot alternative din CH if you're looking at the peak 97 00:09:12,260 --> 00:09:15,680 shape they mostly look the same if you're looking specifically at peaks and 98 00:09:15,680 --> 00:09:20,390 valleys you can kind of tell they're a little different but our experience and 99 00:09:20,390 --> 00:09:25,040 I can see this translating to other labs is if you have a sort of an automated 100 00:09:25,040 --> 00:09:28,280 quantification procedure where the computer will sort of do the work for 101 00:09:28,280 --> 00:09:33,140 you if it's looking for a broad peak in this time range it may not know the 102 00:09:33,140 --> 00:09:39,050 difference between the InP and di di n CH so here this is where 103 00:09:39,050 --> 00:09:45,080 mass spectrum look can really illusi eight the differences the Dench base ion 104 00:09:45,080 --> 00:09:52,550 is 155 vs di NP which is 149 so all really takes is a quick look at the mass 105 00:09:52,550 --> 00:09:56,290 spectrum and you'll be able to tell the difference 106 00:09:56,330 --> 00:10:01,520 another issue we've run into is DN o P vs. dioctyl terephthalate another common 107 00:10:01,520 --> 00:10:07,130 alternative here I have chromatograms of the two of those you can see the 108 00:10:07,130 --> 00:10:11,890 retention time is awfully close 11.15 minutes versus eleven point 100 minutes 109 00:10:11,890 --> 00:10:18,730 and here I've noticed that our our previous settings for our computer 110 00:10:18,730 --> 00:10:24,620 quantification program if the tolerances are empty enough or are wide enough 111 00:10:24,620 --> 00:10:28,130 sorry it may not be able to tell the difference especially since their math 112 00:10:28,130 --> 00:10:31,520 spectrum is pretty similar if you're looking if you're running a sim scan and 113 00:10:31,520 --> 00:10:41,570 looking at the typical DN o P Mass ions do T P covers those as well but if you 114 00:10:41,570 --> 00:10:45,920 do if you're thorough and follow through with your qualitative assessment you'll 115 00:10:45,920 --> 00:10:51,740 see here's our DN o P a typical mass spectrum they speak again is 149 there's 116 00:10:51,740 --> 00:10:58,160 a little bit of 167 and 279 mass ions we'll compare that directly with do T P 117 00:10:58,160 --> 00:11:04,520 and here you can see the the jump and the 261 ion it's almost 50% relative to 118 00:11:04,520 --> 00:11:10,880 149 so if you're looking if you're again if you're doing an automated program you 119 00:11:10,880 --> 00:11:20,570 might get a false positive here if you had do T P so okay so we'll start to 120 00:11:20,570 --> 00:11:25,280 shift into the the rest of the talk here or the rest of the symposium with the 121 00:11:25,280 --> 00:11:29,870 discussion about emerging technologies we'll have a block of speakers today 122 00:11:29,870 --> 00:11:34,700 discussing portable spectroscopy we've started using this as a valley screening 123 00:11:34,700 --> 00:11:43,730 tool a general kind of yes or no might this item have phalates it's when this 124 00:11:43,730 --> 00:11:50,120 law was passed people commonly asked well what's the XRF i'll so if we're 125 00:11:50,120 --> 00:11:56,089 looking for an X or F for lead what's the fal 8 comparable option we have and 126 00:11:56,089 --> 00:12:02,959 this is so far the most promising technology also I'll refer you to this a 127 00:12:02,959 --> 00:12:08,329 paper by Zhang at all last year from chemical communications they developed a 128 00:12:08,329 --> 00:12:12,529 colorimetric test it's a different application they're looking for phalates 129 00:12:12,529 --> 00:12:17,899 in water but I imagine with the right ingenuity and the right research this 130 00:12:17,899 --> 00:12:22,880 might be adapted for toys or childcare articles they use modified gold 131 00:12:22,880 --> 00:12:27,560 nanoparticles that actually changed color and water when my lights were 132 00:12:27,560 --> 00:12:32,899 present and also we're big fans of direct analysis in real time mass 133 00:12:32,899 --> 00:12:37,399 spectrometry I will have a talk on that later so I won't steal too much of that 134 00:12:37,399 --> 00:12:42,290 thunder but it's promising for a screening tool and we think with the 135 00:12:42,290 --> 00:12:47,360 right research possibly also qualification method so just a couple 136 00:12:47,360 --> 00:12:52,610 more sources for information we have CPSC has its own phalates website where 137 00:12:52,610 --> 00:12:57,620 you can get information common questions also we have a lab frequently asked 138 00:12:57,620 --> 00:13:01,009 questions page there if you're interested more in the chronic hazard 139 00:13:01,009 --> 00:13:05,870 advisory panel there's also a website for that they should be issuing a ruling 140 00:13:05,870 --> 00:13:11,930 I believe in that within the calendar year there's currently an ASTM workgroup 141 00:13:11,930 --> 00:13:17,870 focused simply on phalion analysis for low level percentages so I have this 142 00:13:17,870 --> 00:13:22,939 information here and finally EPA has a design for an Environment Program and 143 00:13:22,939 --> 00:13:25,000 they're looking at alternatives to phalates 144 00:13:25,000 --> 00:13:29,839 generally the idea is anyone that's interested in the valley realm and 145 00:13:29,839 --> 00:13:34,189 they're interested in alternatives they can propose alternatives I think they'll 146 00:13:34,189 --> 00:13:38,720 be looking at some toxicology issues so any company that's looking to move this 147 00:13:38,720 --> 00:13:47,900 might be a good website to follow and with that I'll take any questions yeah 148 00:13:47,900 --> 00:13:53,420 oh so he asks what NIST is this is the National Institute for Standards and 149 00:13:53,420 --> 00:14:06,020 Technology yes we consider screening just essentially a tool or a method to 150 00:14:06,020 --> 00:14:11,300 kind of give you a generic yes-or-no answer if phalates are present when we 151 00:14:11,300 --> 00:14:14,750 look as a screening tool for if we're looking for lead we use x-ray 152 00:14:14,750 --> 00:14:19,490 fluorescence as a screening tool this will give us like essentially 30 seconds 153 00:14:19,490 --> 00:14:24,050 to a minute we have a general idea of if light is present or there so that's sort 154 00:14:24,050 --> 00:14:38,779 of the itinerary we're looking for with valleys he asked if there's a acceptable 155 00:14:38,779 --> 00:14:43,550 level for screening as far as false positives or not I think that's to be 156 00:14:43,550 --> 00:14:47,960 determined you know we're trying to work with its each technology will have its 157 00:14:47,960 --> 00:14:52,520 own limitations and you know I think the best we can get on any regards will 158 00:14:52,520 --> 00:14:57,650 we'll work with for now I mean for a generic tool if you know are the limits 159 00:14:57,650 --> 00:15:02,600 0.1% and I think for a final screening tool it will be able to it'll need to be 160 00:15:02,600 --> 00:15:07,850 able to reach that but there might be different ways to adapt back technology 161 00:15:07,850 --> 00:15:16,400 or different applications to try and use that to your best advantage hi I'm Joel 162 00:15:16,400 --> 00:15:19,850 rectum the chemistry division director here I just wanted to add to that the 163 00:15:19,850 --> 00:15:24,529 the what's needed from a screening tool depends somewhat on what it's being used 164 00:15:24,529 --> 00:15:34,029 for as well so affirm we have a speaker here from BASF today BASF produces 165 00:15:34,029 --> 00:15:41,660 phthalates there need to screen for four products you know for perhaps impurities 166 00:15:41,660 --> 00:15:45,380 in their line are different than the needs that we have as a regulatory 167 00:15:45,380 --> 00:15:50,750 agency or a manufacturer who might look to do screening in between their full 168 00:15:50,750 --> 00:15:56,120 tests so you know there can still be room for for these screening methods 169 00:15:56,120 --> 00:16:02,440 where it makes sense in a particular end use 170 00:16:08,380 --> 00:16:29,740 I'm sorry oh yeah we we consider screen printing applicable to regulation yes 171 00:16:37,410 --> 00:16:43,829 well I think we're we'd like to work towards that point it would be ideal but 172 00:16:43,829 --> 00:16:47,899 we don't think it's at that point yet 173 00:16:55,429 --> 00:17:02,039 yeah we think they've been used for oh I'm sorry has do TPD a little 174 00:17:02,039 --> 00:17:08,039 terephthalate been in use often yes we we have we've we're familiar with it we 175 00:17:08,039 --> 00:17:11,509 think it's been used and used for a while 176 00:17:15,449 --> 00:17:19,679 that's not my I'm not I can't answer that that that would be a good question 177 00:17:19,679 --> 00:17:26,629 for the EPA design for alternatives and and the chronic hazard advisory panel 178 00:17:28,100 --> 00:17:33,870 all right great why don't we move along our next speaker is Raphael Costa from 179 00:17:33,870 --> 00:17:36,320 Agilent 180 00:17:45,590 --> 00:17:51,270 thank you thank you Matt for inviting me here to 181 00:17:51,270 --> 00:17:55,020 this symposium is very exciting for us to be here and what I'm gonna do today 182 00:17:55,020 --> 00:17:59,100 is share with you some of the different mass spectrometry techniques that may 183 00:17:59,100 --> 00:18:06,050 aid you in solving that problem of contamination or library matching or 184 00:18:06,050 --> 00:18:10,770 retention times matching up what are some of the tools that we could use and 185 00:18:10,770 --> 00:18:14,040 what are some of the applications that admins are our scientists in the field 186 00:18:14,040 --> 00:18:19,170 have developed to meet this growing need of phthalates and consumer products and 187 00:18:19,170 --> 00:18:24,750 specific in toys and in particular so I'll go through some of the GCMs 188 00:18:24,750 --> 00:18:29,340 portfolio the different technologies of different flavors of mass spectrometry 189 00:18:29,340 --> 00:18:34,170 that could aid you in identifying phthalates in a way that gives you that 190 00:18:34,170 --> 00:18:37,770 much more confidence in your lab I'll go throughout the application notes 191 00:18:37,770 --> 00:18:41,190 developed by our scientist in the field and then we'll go through some of the 192 00:18:41,190 --> 00:18:45,000 ongoing work that we internally at Agilent are working with to solve this 193 00:18:45,000 --> 00:18:49,740 problem of trying to reach the levels required and the different technologies 194 00:18:49,740 --> 00:18:54,930 and level of confidence in your results so for example the Agilent GCMs our 195 00:18:54,930 --> 00:18:59,970 portfolio includes not only single quartz ion traps mobile mass 196 00:18:59,970 --> 00:19:06,200 spectrometers as well as high-end triple quads and now cute off technology for 197 00:19:06,200 --> 00:19:10,500 mass spectrometry what I will do is I'll say how each of these different 198 00:19:10,500 --> 00:19:15,210 techniques apply to your particular analysis what are some of the extra 199 00:19:15,210 --> 00:19:19,830 information that you get from each individual technique so for example we 200 00:19:19,830 --> 00:19:25,560 know we have here the usual suspects of the phthalates of interest but their 201 00:19:25,560 --> 00:19:29,600 caste number their molecular weights and there are corresponding ions for sim 202 00:19:29,600 --> 00:19:35,400 analysis the typical GC conditions that was used in this particular application 203 00:19:35,400 --> 00:19:42,660 was a very mirror column 0.25 0.25 micron db5 ultra inner column that this 204 00:19:42,660 --> 00:19:46,590 will allow allow you to have more the ultra nurnies allows you to have more 205 00:19:46,590 --> 00:19:51,480 runs per sample let's bleed in your chromatograms since 206 00:19:51,480 --> 00:19:57,660 our mass specs are very sensitive there is a split ratio of 20 to 1 to avoid 207 00:19:57,660 --> 00:20:01,890 contamination and column overload carrier gases helium 208 00:20:01,890 --> 00:20:06,840 however we're noticing that customers are asking us hey can we use hydrogen 209 00:20:06,840 --> 00:20:11,340 for analysis and that's something that you definitely can't do with your single 210 00:20:11,340 --> 00:20:17,280 quads GCMs however we're trying to see how that could aid you more but the cost 211 00:20:17,280 --> 00:20:21,030 of helium as you may or may not know is going up drastically recently and we're 212 00:20:21,030 --> 00:20:24,450 trying to address that in terms of uh how can we take advantage of the 213 00:20:24,450 --> 00:20:28,830 properties of hydrogen as carrier gas which is not a new thing in Europe they 214 00:20:28,830 --> 00:20:31,920 currently use that's the carrier gas of choice hope 215 00:20:31,920 --> 00:20:37,050 and we're trying to make our us customers aware of this as well not only 216 00:20:37,050 --> 00:20:42,150 do you get the benefits of maybe having a reducing your cost of analysis by 217 00:20:42,150 --> 00:20:46,320 having hydrogen through a hydrogen generator in your lab but also have 218 00:20:46,320 --> 00:20:50,040 faster chromatography so we definitely want to ensure that you're aware of 219 00:20:50,040 --> 00:20:54,330 though of that the possibility that that could bring to your labs well for 220 00:20:54,330 --> 00:21:00,690 example here we have a total iron chromatogram of a pacifier extract on 221 00:21:00,690 --> 00:21:05,310 spiked and spiked with two parts per million phthalic mixture on top you see 222 00:21:05,310 --> 00:21:10,830 the mutilated hydroxy toluene as the main peak in the pacifier however when 223 00:21:10,830 --> 00:21:16,800 we spiked it at 2 ppm we're still able to see this in matrix uh very nicely so 224 00:21:16,800 --> 00:21:23,430 again not the DI MP and the DI p di DP are very uh a little bit less sensitive 225 00:21:23,430 --> 00:21:29,970 to particular analysis of VII however there are things that that are mentioned 226 00:21:29,970 --> 00:21:34,740 throughout my presentation that may allow you to see higher levels of these 227 00:21:34,740 --> 00:21:40,920 particular compás and we'll go through that as well okay so for example you're 228 00:21:40,920 --> 00:21:44,190 talking about sample cleanup and contamination one possible way to avoid 229 00:21:44,190 --> 00:21:49,440 contamination may be to use the SPME or solid phase microextraction in your 230 00:21:49,440 --> 00:21:53,820 analysis which reduces some of the the non analytes of interest of all the 231 00:21:53,820 --> 00:21:57,930 matrix of your particular toys or analysis that would allow you to have 232 00:21:57,930 --> 00:22:02,130 cleaner chromatograms and less contamination and more throughput per 233 00:22:02,130 --> 00:22:08,160 samples went through GCMs okay so for example so these for these particular 234 00:22:08,160 --> 00:22:11,670 compounds of interest these phthalates of interest we are able to regional of 235 00:22:11,670 --> 00:22:15,960 in the level of from 0.25 milligrams per litre to 10 236 00:22:15,960 --> 00:22:20,730 with a linear dynamic range and we have individual retention times for these so 237 00:22:20,730 --> 00:22:26,029 we could definitely identify them not only based on retention time but also on 238 00:22:26,029 --> 00:22:30,960 their spectrum as well with the GCMs one of the things that you may be that you 239 00:22:30,960 --> 00:22:34,110 may have is if you're doing high throughput analysis in your lab and you 240 00:22:34,110 --> 00:22:37,940 want to ensure have one method through all your lab you want to ensure that you 241 00:22:37,940 --> 00:22:43,230 implore something that we call retention time locking how many of you are used 242 00:22:43,230 --> 00:22:48,059 GCMs for analysis of valets today in your labs how many of you have an 243 00:22:48,059 --> 00:22:52,440 Agilent system in your lab and how many of you are using retention time locking 244 00:22:52,440 --> 00:22:56,519 and your instruments so that each retention time in each instrument that 245 00:22:56,519 --> 00:23:02,369 you have with the same method is exactly the same one okay I'll talk through that 246 00:23:02,369 --> 00:23:05,999 I'll go through that in my presentation and how that could aid you and having 247 00:23:05,999 --> 00:23:10,080 that much more confidence it's one of the hidden secrets that we have and we 248 00:23:10,080 --> 00:23:13,139 love my job here today is to make you aware of these features that may make 249 00:23:13,139 --> 00:23:16,529 your life a little easier in the lab when you're analyzing phthalates or 250 00:23:16,529 --> 00:23:24,600 other compounds of interest as well okay so I'll go here up so for example let's 251 00:23:24,600 --> 00:23:27,960 say you want to take yours your lab method and you want to take it in the 252 00:23:27,960 --> 00:23:32,009 field in the back of a mobile lab and you want to test at the point of sale of 253 00:23:32,009 --> 00:23:36,389 our particular product you could do that with our agilent of 50 975 t for 254 00:23:36,389 --> 00:23:40,679 transportable which implores LTM technology essentially what you have now 255 00:23:40,679 --> 00:23:44,519 here is you have the same mass spectrometer that you're used to in your 256 00:23:44,519 --> 00:23:48,450 lab and you're able to take it in the field at 1/3 of the footprint and half 257 00:23:48,450 --> 00:23:53,399 the power consumption you could run it in as part of a mobile lab if you're 258 00:23:53,399 --> 00:23:57,690 looking for phalates in the field for example and essentially as I mentioned 259 00:23:57,690 --> 00:24:03,330 before the otm technology what it does is is essentially by heated oven so 260 00:24:03,330 --> 00:24:06,570 essentially your capillary column is inductively coupled with a heater that 261 00:24:06,570 --> 00:24:11,399 allows the maximum a lot of heat transfer very efficient efficiently so 262 00:24:11,399 --> 00:24:15,749 now you have faster heating and cooling times so your chromatography males will 263 00:24:15,749 --> 00:24:19,559 also improve you have more sample throughput now chromatograms that will 264 00:24:19,559 --> 00:24:24,539 take you 20 to 25 minutes for analysis may take you five or less minutes for 265 00:24:24,539 --> 00:24:26,530 the same analysis and still having the same 266 00:24:26,530 --> 00:24:30,790 resolution and sensitivity so again that's that's something for you if 267 00:24:30,790 --> 00:24:33,040 you're not aware of for you to think about if you're thinking about doing 268 00:24:33,040 --> 00:24:42,730 mobile lab applications of phthalates in the field okay so one of the things that 269 00:24:42,730 --> 00:24:46,510 they imagined that we that we recently were excited about is the introduction 270 00:24:46,510 --> 00:24:53,110 of ion trap technology for GCMs and one of the benefits that you receive with 271 00:24:53,110 --> 00:24:57,010 ion trap technologies the ability to do multiple I announced a ssin techniques 272 00:24:57,010 --> 00:25:00,790 within the same chromatogram so for example for an ion for particular 273 00:25:00,790 --> 00:25:06,670 phthalates that may not be as responsive to e.i analysis you could do a CI and 274 00:25:06,670 --> 00:25:09,730 Alice chemical ionic station on the same compound in the same run in same 275 00:25:09,730 --> 00:25:14,170 chromatogram so you can switch from e-i to CI without changing the source in the 276 00:25:14,170 --> 00:25:19,720 same run which will allow you greater sensitivity and specificity for analytes 277 00:25:19,720 --> 00:25:23,850 of interest and I'll show a particular example of that in this case we have a 278 00:25:23,850 --> 00:25:32,500 VI MP and the IPP the IDP and we have them in AI and CI if you notice the e I 279 00:25:32,500 --> 00:25:39,730 expect from shows the classical Mass 149 s as the after parent peak however if we 280 00:25:39,730 --> 00:25:46,840 use CI with MTBE liquid MTBE were able to differentiate the two now base you 281 00:25:46,840 --> 00:25:53,770 see have the molecular ion be the parent peak and now we have 419 and for 47 okay 282 00:25:53,770 --> 00:25:57,580 the molecular ions in a higher intensity so if this is something that there may 283 00:25:57,580 --> 00:26:01,870 be interest of you for you to identify the two you have the flexibility of 284 00:26:01,870 --> 00:26:08,050 doing CI a liquid CI with MTBE to allow you to differentiate those two and give 285 00:26:08,050 --> 00:26:12,220 you that much more degrees of confidence okay and again this is coupled to the 286 00:26:12,220 --> 00:26:17,380 same 7890 GCC pneumatics are you used to on the front end just a different 287 00:26:17,380 --> 00:26:21,970 ionization technique iron trap technology on the back end okay so here 288 00:26:21,970 --> 00:26:31,060 for example in terms of calibration curve for bbp and VBP able to go down to 289 00:26:31,060 --> 00:26:38,640 levels of one parts per billion or less okay so now we mentioned the other 290 00:26:38,640 --> 00:26:42,420 labor of mass spectrometer that can be applied to the fellows analysis involves 291 00:26:42,420 --> 00:26:46,620 the use of a triple quadrupole GCMs and I go briefly into how that operates 292 00:26:46,620 --> 00:26:51,360 currently in our lab in and Santa Clara are one of our applications our chemists 293 00:26:51,360 --> 00:26:56,070 and in conjunction with dois we're frontier we have a paralyzer system and 294 00:26:56,070 --> 00:27:02,070 you might hear some of that today but essentially we're analyzing phthalates 295 00:27:02,070 --> 00:27:06,180 using triple quadruple GCMs and that gives us a different degrees of 296 00:27:06,180 --> 00:27:09,660 confidence and also lower sensitivity and there's an application now coming 297 00:27:09,660 --> 00:27:13,020 soon with that information but I talked briefly of some of the preliminary 298 00:27:13,020 --> 00:27:17,730 results that we that we have obtained so let me give you a little brief overview 299 00:27:17,730 --> 00:27:22,370 of how triple quadrupole GCMs operates from for example you have your typical 300 00:27:22,370 --> 00:27:27,750 spectrum so you ionize your samples they give you any I mode in this particular 301 00:27:27,750 --> 00:27:31,800 example you get a classical spectrum okay everything is ionized broken down 302 00:27:31,800 --> 00:27:39,720 into individual components however through the first quadrupole we isolate 303 00:27:39,720 --> 00:27:44,640 one ion in this case we select the most intense ion which is 210 we'll select 304 00:27:44,640 --> 00:27:50,250 that ion in this particular case and your Simenon die on that iron you pass 305 00:27:50,250 --> 00:27:53,460 it that iron through a collision cell hit it with some energy and some 306 00:27:53,460 --> 00:27:58,380 collision gases you're able to break down that ion even further into two 307 00:27:58,380 --> 00:28:02,280 individual components and then you can monitor multiple ions from that 308 00:28:02,280 --> 00:28:06,990 secondary fragmentation in this case will be a transition of for example to 309 00:28:06,990 --> 00:28:12,480 10 go into 158 and 191 which may give you that much more fragmentation and 310 00:28:12,480 --> 00:28:17,760 identification for some of the trouble and lights of interest okay so in this 311 00:28:17,760 --> 00:28:22,680 case we have a mrm chink thick total iron chromatogram in of phthalates and 312 00:28:22,680 --> 00:28:30,630 lemon oil okay this is this is the mrm take the e i spectra of the NOP and the 313 00:28:30,630 --> 00:28:35,550 triple quad and you can see that the iron ratios are very similar to your 314 00:28:35,550 --> 00:28:41,070 nest libraries that you're used to and we have developed transition we have 315 00:28:41,070 --> 00:28:44,880 developed mrm translation multiple reaction monitored transaction for our 316 00:28:44,880 --> 00:28:49,560 different values of interest where now if you're interested in having more 317 00:28:49,560 --> 00:28:54,809 information on your salads and in that one particular ion with some 318 00:28:54,809 --> 00:29:00,450 energy and a collision flow you're able to get to individual transitions one for 319 00:29:00,450 --> 00:29:05,490 quantitation and one for quality ssin and you're able to develop a set up find 320 00:29:05,490 --> 00:29:08,970 ratios for each particular transition therefore the ohmmeter particular 321 00:29:08,970 --> 00:29:13,080 requirements for your quantitation this decreases your for your false positives 322 00:29:13,080 --> 00:29:15,840 was met what it's talking about about false positives being a big problem 323 00:29:15,840 --> 00:29:18,600 ms/ms could potentially solve that for you 324 00:29:18,600 --> 00:29:26,130 reduces the amount of false positives in your thallus analysis okay now for for 325 00:29:26,130 --> 00:29:30,990 higher quality data and for more interesting results for example you 326 00:29:30,990 --> 00:29:36,720 could take the power of Q Tov mass accuracy and high resolution for the 327 00:29:36,720 --> 00:29:41,640 analysis of valleys in high matrix you have the ability to do ms/ms and E I as 328 00:29:41,640 --> 00:29:49,440 well and in this case what we have is our traditional triple quad which is 329 00:29:49,440 --> 00:29:53,970 based on your single quad mass spectrometer that you used to currently 330 00:29:53,970 --> 00:29:57,049 use it in your lab we took that technology a step further and 331 00:29:57,049 --> 00:30:01,409 incorporated our trouble quadrant mass spectrometer to our tough mass 332 00:30:01,409 --> 00:30:05,580 spectrometer that we have in our we had in our LC world that we made this 333 00:30:05,580 --> 00:30:09,330 marriage of a cute off so now you have the ability of doing full scan high 334 00:30:09,330 --> 00:30:15,690 resolution high mass accuracy less than 5 ppm mass accuracy and you know I'll 335 00:30:15,690 --> 00:30:18,900 show you what that gives you what level of information that provides you in a 336 00:30:18,900 --> 00:30:24,780 second so for example if you're used to looking at your typical single quad mass 337 00:30:24,780 --> 00:30:29,970 spectrometer and we'll look at Matt's mass 604 what you see in the red is your 338 00:30:29,970 --> 00:30:35,400 typical spectrum however it with the tough technology you're able to really 339 00:30:35,400 --> 00:30:41,460 resolve the 613 and the 614 the 649 and you get accurate masses to the point 340 00:30:41,460 --> 00:30:44,820 that you have more resolution and when we talk about resolution we're talking 341 00:30:44,820 --> 00:30:49,230 about the space between the two the two different isotopes there let you see 342 00:30:49,230 --> 00:30:53,340 okay so that's one level of confidence that will also decrease your false 343 00:30:53,340 --> 00:30:56,100 positive or negative so if you have a high matrix and things that may be 344 00:30:56,100 --> 00:31:01,260 interfering q top technology with the high- accuracy and resolution may give 345 00:31:01,260 --> 00:31:04,840 you that extra level of confidence of able to seize the needle in the haystack 346 00:31:04,840 --> 00:31:12,850 a little bit better okay so for example your typical mass spectrometer has a has 347 00:31:12,850 --> 00:31:20,920 a insurgency let's say 0.3 a.m. use and for mass 271 for 9:00 8:00 a.m. you 348 00:31:20,920 --> 00:31:26,740 there are 7600 compounds that are possible based on that mass insurgency 349 00:31:26,740 --> 00:31:33,250 of 1000 ppm as the as the young certainty decreases let's say to a level 350 00:31:33,250 --> 00:31:39,910 of 1 ppm parts per million now you have 11 possible compounds that are possible 351 00:31:39,910 --> 00:31:45,280 with that particular ion of interest so that's where the again reduces your 352 00:31:45,280 --> 00:31:51,520 false positives or high level of degree of confidence in your analysis also too 353 00:31:51,520 --> 00:31:57,220 so those of you that are using our our mass spectrometers for the analysis of 354 00:31:57,220 --> 00:32:01,720 phthalates retention time locking is very important and as Matt discussed 355 00:32:01,720 --> 00:32:05,830 earlier retention time is one of the requirements for for the methods of 356 00:32:05,830 --> 00:32:11,830 analysis having retention time locking allows you to have one method on one 357 00:32:11,830 --> 00:32:15,580 mass spectrometer transfer that method to a second mass spectrometer and 358 00:32:15,580 --> 00:32:18,790 they'll have the exact retention time okay 359 00:32:18,790 --> 00:32:22,300 and whether you perform current maintenance or not you're able to just 360 00:32:22,300 --> 00:32:26,170 we lock the method it's very simple to do it just takes five injection you 361 00:32:26,170 --> 00:32:29,230 could do it overnight or over a lunch break 362 00:32:29,230 --> 00:32:33,970 or right you can do it actually while you are commissioning your instruments 363 00:32:33,970 --> 00:32:38,290 for analysis doing your performance check you take one analyte of interest 364 00:32:38,290 --> 00:32:43,150 you look for that ion what it does is retention time locking what it does it 365 00:32:43,150 --> 00:32:51,070 incorporates all the possible variations in column length pressure or whether you 366 00:32:51,070 --> 00:32:55,270 have a difference of a few millimeters going into the inlet or not it takes all 367 00:32:55,270 --> 00:32:59,559 the possible errors incorporates them into a pressure error and allows you to 368 00:32:59,559 --> 00:33:04,030 match your retention times with fermented transfer okay so in any system 369 00:33:04,030 --> 00:33:07,360 across this so you have a lab and the East Coast the west coast the retention 370 00:33:07,360 --> 00:33:12,670 times will be the same if we're trying to match the new phthalates analytes of 371 00:33:12,670 --> 00:33:14,710 interest so that's yes you have a question 372 00:33:14,710 --> 00:33:18,510 that within the same historian if you were to replace a Kabul say could you 373 00:33:18,510 --> 00:33:28,180 pull the data up and then switch out the column and then run that software runs 374 00:33:28,180 --> 00:33:33,539 and then have yes yes you can do that while you change 375 00:33:33,539 --> 00:33:38,610 count that retention time if you want the IP to be at 11 minutes 11 point oo 1 376 00:33:38,610 --> 00:33:41,010 minute it will be at 11.1 minutes in this 377 00:33:41,010 --> 00:33:43,760 instrument and that instrument will you change your column every day all day 378 00:33:43,760 --> 00:33:47,760 year after year and it's free is included in your mouth and your camp 379 00:33:47,760 --> 00:33:51,690 station software it's a button if you go in your method there will be an option 380 00:33:51,690 --> 00:33:56,910 instrument retention time lock and I'll ask you to put a violin in a particular 381 00:33:56,910 --> 00:34:00,870 position position one it'll do five runs at five different pressures and they 382 00:34:00,870 --> 00:34:04,230 don't make a calibration of pressure versus retention time and then will 383 00:34:04,230 --> 00:34:08,220 retain that calibration file and then you're able to your mentor will be 384 00:34:08,220 --> 00:34:11,429 locked to a particular compound so if you want to lock whether on your 385 00:34:11,429 --> 00:34:15,540 internal standard or whatever it is you can lock in your internal standard and 386 00:34:15,540 --> 00:34:19,350 there was those retention times will match that way you won't have to 387 00:34:19,350 --> 00:34:23,159 question it this style aid or is it that valid no because it's retention times 388 00:34:23,159 --> 00:34:29,820 will match all day every day okay again and retention time lock and it's 389 00:34:29,820 --> 00:34:35,730 available everything from from our 7059 75e single quad to our cubes off okay 390 00:34:35,730 --> 00:34:39,720 even to your mobile lab if you want to retention time in your mobile lab you 391 00:34:39,720 --> 00:34:45,899 have that flexibility so again one of things I want to emphasize this and the 392 00:34:45,899 --> 00:34:49,500 other speakers will go into different other front ends that that made you an 393 00:34:49,500 --> 00:34:52,619 analysis but I wanted to focus in the different capabilities is the take-home 394 00:34:52,619 --> 00:34:56,550 message here is that if you're looking for routine analysis and you want to do 395 00:34:56,550 --> 00:35:00,600 next and this is the convolution our single quad will be do a great job if 396 00:35:00,600 --> 00:35:07,500 you haven't promised with hi matrix interference then there's that's when a 397 00:35:07,500 --> 00:35:12,480 triple quad may be more suitable for the analysis because we'll give you that mrm 398 00:35:12,480 --> 00:35:15,359 transition of one iron going through different transitions with two different 399 00:35:15,359 --> 00:35:19,710 iron ratios so you get more degrees of confidence and if going from E AI to CI 400 00:35:19,710 --> 00:35:22,980 is something that you really want to do for your analysis to give you that peace 401 00:35:22,980 --> 00:35:26,070 of mind and give you that much more confidence in your results that's when 402 00:35:26,070 --> 00:35:32,430 an iron trap with like liquid CI what MTBE may may aid you even more I just 403 00:35:32,430 --> 00:35:36,510 wanna the references up you can look these up in our application notes and 404 00:35:36,510 --> 00:35:39,210 there's more to come especially specifically on the cubes off 405 00:35:39,210 --> 00:35:43,530 and the triple quad analysis and I want to give a special thanks to our 406 00:35:43,530 --> 00:35:47,490 scientists that have worked on this Stefan Bowman fred fighter herm robert 407 00:35:47,490 --> 00:35:50,700 kubis and matt thank you for inviting us to be here today 408 00:35:50,700 --> 00:35:55,670 any questions yes 409 00:36:17,650 --> 00:36:24,980 yes oh yes the question was whether we could use a ammonia CI reagent ah for 410 00:36:24,980 --> 00:36:28,280 the analysis of phthalates and the answer is yes you can in this particular 411 00:36:28,280 --> 00:36:32,240 case I was MTBE was used for through the analysis but you could definitely use 412 00:36:32,240 --> 00:36:35,540 ammonia or even methane of that which but ammonia temps tends to be more 413 00:36:35,540 --> 00:36:40,100 sensitive in terms of CI from what we've seen in particular for phthalates yes 414 00:36:40,100 --> 00:36:44,920 good question any any other questions yes 415 00:36:45,580 --> 00:36:51,110 thus we tension time lock work for multiple analytes the answer is yes what 416 00:36:51,110 --> 00:36:55,280 we tension time locking does is it takes one particular analyte and typically in 417 00:36:55,280 --> 00:36:59,390 the middle of your chromatogram so you pick whatever analytes and your lock on 418 00:36:59,390 --> 00:37:03,410 that and everything else is gonna be relative to that so if you if this 419 00:37:03,410 --> 00:37:06,980 analyte match everything else should match depending then you have a good 420 00:37:06,980 --> 00:37:10,790 column in your column is now bad so yes so all the components will be retention 421 00:37:10,790 --> 00:37:16,060 time locked but you only like a want to compound everything else is relative 422 00:37:27,520 --> 00:37:31,820 what broader Peaks retention time locking what is gonna do is you're still 423 00:37:31,820 --> 00:37:36,050 gonna have that broad peak however that broad peak will be at the same time so 424 00:37:36,050 --> 00:37:38,360 that doesn't say essentially what's gonna happen it's gonna add your your 425 00:37:38,360 --> 00:37:41,270 your chromatography in terms of resolution but it will give you that 426 00:37:41,270 --> 00:37:46,130 same time for that blob of gram that you have for the InP yes good question yes 427 00:37:46,130 --> 00:37:48,760 another question 428 00:38:00,560 --> 00:38:05,580 okay the question is is our triple Quadra trapping or ions and the answer 429 00:38:05,580 --> 00:38:09,840 is it's not really trap it is scanning scanning very fast and it's taking a 430 00:38:09,840 --> 00:38:14,490 selectively passing ions that we select that we want so for example in this 431 00:38:14,490 --> 00:38:20,040 particular example that I showed let's say you want to isolate 149 I've won a 432 00:38:20,040 --> 00:38:24,810 and 149 will go through the quad it'll reach a collision cell once it reaches 433 00:38:24,810 --> 00:38:28,710 the collision cell it will be hit with a particular energy typically between ten 434 00:38:28,710 --> 00:38:32,820 and fifteen volts electron volt and a collision gas and from there we'll have 435 00:38:32,820 --> 00:38:35,970 two different transitions that we can monitor typically the most the two 436 00:38:35,970 --> 00:38:41,150 strongest transitions to give you that much more of degrees of confidence 437 00:38:50,720 --> 00:38:54,410 the question was where is there any gain-of-function automatic gain function 438 00:38:54,410 --> 00:38:58,040 the answer is there is no automatic gain however for compounds of interest you 439 00:38:58,040 --> 00:39:02,000 could adjust the gains in the different time segments so for example for 440 00:39:02,000 --> 00:39:05,750 analytes that are maybe less sensitive you may adjust the gain at that 441 00:39:05,750 --> 00:39:19,369 particular moment in time thank you so much up next we have Bob Freeman from 442 00:39:19,369 --> 00:39:34,760 frontier labs all right good morning I'd like to thank Matt for the opportunity 443 00:39:34,760 --> 00:39:38,030 to talk about the method it's been in development now for about two or three 444 00:39:38,030 --> 00:39:44,060 years about about three years ago we started at the ASTM D 20 former 445 00:39:44,060 --> 00:39:50,359 committee to look at low-level phthalates in polyvinyl chloride and for 446 00:39:50,359 --> 00:39:53,480 the past two or three years this is what we focused on we've done two sets of 447 00:39:53,480 --> 00:39:58,280 round-robin samples and we've done independent validation study with some 448 00:39:58,280 --> 00:40:01,730 laboratories so I'd like to give you just a status report on where that 449 00:40:01,730 --> 00:40:05,930 method is give you a little bit of data and then I'll also like to kind of 450 00:40:05,930 --> 00:40:10,369 address the issue of phthalates in hold because you'll notice that for those 451 00:40:10,369 --> 00:40:14,660 people who do work on methods phthalates our particular problem because the fact 452 00:40:14,660 --> 00:40:18,800 is that the method no longer is what what it was designed to do we started 453 00:40:18,800 --> 00:40:23,540 off with toys and we started off with six phthalates and in the last two or 454 00:40:23,540 --> 00:40:26,990 three years now all of a sudden we're looking at electronic products we're 455 00:40:26,990 --> 00:40:32,420 looking at food containers we're looking at a whole variety of different matrices 456 00:40:32,420 --> 00:40:36,440 and you'll notice that we've gone from six phthalates till now there's interest 457 00:40:36,440 --> 00:40:40,609 in more than six in some cases fifteen and sixteen phthalates so whereas we 458 00:40:40,609 --> 00:40:45,260 started with toys and consumer products now we have to work the stakeholders 459 00:40:45,260 --> 00:40:51,589 include formulators past recyclers manufacturers retailers consumers all of 460 00:40:51,589 --> 00:40:54,829 a sudden everybody's interested in phthalates and what we find out is 461 00:40:54,829 --> 00:40:58,670 interesting that lights all over the world and this is all well and good 462 00:40:58,670 --> 00:41:03,140 except for now you notice that the list is starting to expand a little bit and 463 00:41:03,140 --> 00:41:06,530 so some of the electronics News have included things like dye 464 00:41:06,530 --> 00:41:10,520 isobutyl phthalates which is a which is a plasticizer that's 465 00:41:10,520 --> 00:41:16,400 not too not too uncommon it's a low-cost replacement for DBP so now we've gone 466 00:41:16,400 --> 00:41:22,579 from from three regulated phthalates to a possible six phthalates seventh a 467 00:41:22,579 --> 00:41:27,109 lates and you can see we're having the typical encounter here and that is as we 468 00:41:27,109 --> 00:41:31,010 develop the method we officer may include more and more matrices and as we 469 00:41:31,010 --> 00:41:34,069 do that we want more and more compounds and as we do that of course we want more 470 00:41:34,069 --> 00:41:38,809 and more sensitivity and so those of us are workout methods this is a continuing 471 00:41:38,809 --> 00:41:43,490 problem there's even there's even individual countries that are writing 472 00:41:43,490 --> 00:41:48,740 general methods that have promulgated these most of them in 2011 and these are 473 00:41:48,740 --> 00:41:52,460 just mentioning things like all products containing phthalates I mean that's a 474 00:41:52,460 --> 00:41:59,660 pretty general description for method to address and because now you hear more 475 00:41:59,660 --> 00:42:02,799 and more about the countries not being important the global global 476 00:42:02,799 --> 00:42:06,770 international corporations really being the boundaries there are many 477 00:42:06,770 --> 00:42:11,869 corporations that work on a global scale and have their own in-house methods and 478 00:42:11,869 --> 00:42:15,619 in-house list of compounds and in Houston Texas and limits for various 479 00:42:15,619 --> 00:42:18,920 number of phthalates and so these are just some of the electronics companies 480 00:42:18,920 --> 00:42:23,990 that we know I'm familiar with that are working on phthalates in recycled 481 00:42:23,990 --> 00:42:29,540 plastics and different lists and we work on right now so we've gone from in the 482 00:42:29,540 --> 00:42:35,030 beginning the ASTM method is PVC and six compounds so now we're talking about 483 00:42:35,030 --> 00:42:40,400 maybe fifteen or sixteen and way beyond PVC so let me back up a little bit talk 484 00:42:40,400 --> 00:42:43,880 about the ASTM methods we're looking for a standard practice 485 00:42:43,880 --> 00:42:47,900 for the determination of low level phthalates and polyvinyl chloride and 486 00:42:47,900 --> 00:42:52,369 the method that seems to give us the best results this thermal desorption GC 487 00:42:52,369 --> 00:42:56,750 mass spec so there's really five steps in this method and this is the most 488 00:42:56,750 --> 00:43:00,530 difficult step to step right here called sample homogeneity because when you take 489 00:43:00,530 --> 00:43:04,670 a toy for example different parts of that toy are made of four different 490 00:43:04,670 --> 00:43:08,510 plastics and each of those different parts of plastics can have a different 491 00:43:08,510 --> 00:43:12,049 level of phthalates and so I would say if I if I were to look at the overall 492 00:43:12,049 --> 00:43:17,150 scope of analyzing for phthalates in materials the biggest problem is a 493 00:43:17,150 --> 00:43:21,290 homogeneous because if I take this toy apart I can 494 00:43:21,290 --> 00:43:23,360 get three different numbers some of them are good and some of them are a little 495 00:43:23,360 --> 00:43:27,380 bit higher a circuit board forces the same problem a food container proposes 496 00:43:27,380 --> 00:43:30,950 the same problem and so on and so forth so this is the single most difficult 497 00:43:30,950 --> 00:43:36,410 thing to do and that is to get a homogeneous sample that sounds nice to 498 00:43:36,410 --> 00:43:39,980 say crowd milling you go into laboratories that do crowd milling and 499 00:43:39,980 --> 00:43:44,930 contamination crosstalk between Crowell Mills is ever-present and so one of the 500 00:43:44,930 --> 00:43:48,860 problems with phthalates as we as we mentioned here is contamination well 501 00:43:48,860 --> 00:43:53,300 right off the bat if you're using one crowd milled into five toys the 502 00:43:53,300 --> 00:43:59,960 possibility for cross-contamination is very high this is the toughest step but 503 00:43:59,960 --> 00:44:04,700 the method that the the thumb of the ASTM method for based on thermal 504 00:44:04,700 --> 00:44:08,240 desorption GC mass spec uses two solutions one is just a standard 505 00:44:08,240 --> 00:44:12,320 solution of the phthalates of interest and the other is the sample itself which 506 00:44:12,320 --> 00:44:16,880 is dissolved in tetrahydrofuran so this is the there's only two solutions 507 00:44:16,880 --> 00:44:22,490 involved the injection is simply placing these solutions in a small container 508 00:44:22,490 --> 00:44:27,020 raising the temperature the containers such that the target compounds evolve or 509 00:44:27,020 --> 00:44:31,250 make out or externally extracted and analyzing just that portion of the 510 00:44:31,250 --> 00:44:36,500 sample that contains the phthalates separation is done by a standard 30 511 00:44:36,500 --> 00:44:41,780 meter db5 or 5% phenol column and detector you can pick up most of the 512 00:44:41,780 --> 00:44:46,100 work we've been done has been done with scanning ms several of the validation 513 00:44:46,100 --> 00:44:51,170 labs used si MMS you can use quadruple crippled quads you can use negative ion 514 00:44:51,170 --> 00:44:57,800 CI this is the area where the method seems to be the most applicable and that 515 00:44:57,800 --> 00:45:02,240 is this is this is unlike the first talk this is how to get the sampler prepared 516 00:45:02,240 --> 00:45:08,630 and how to get the sample into the column okay what column you use is up to 517 00:45:08,630 --> 00:45:13,090 you it's independent of the column choice what sort of detection algorithm 518 00:45:13,090 --> 00:45:19,400 system you want to use this up to you so this is the sample prep the whole idea 519 00:45:19,400 --> 00:45:21,830 here is to give her the solvent to get rid of the glassware 520 00:45:21,830 --> 00:45:25,220 because I've gone into laboratories and who do this and they'll tell me 521 00:45:25,220 --> 00:45:30,020 oftentimes they spend more time cleaning Sox lists and using Sox's your salads 522 00:45:30,020 --> 00:45:33,559 are difficult to get rid of and so what we do here is we start off 523 00:45:33,559 --> 00:45:36,740 with the product some sort of material could be a circuit board could be a duct 524 00:45:36,740 --> 00:45:41,240 we all like ducts you Crowl millet you want the smallest pieces you can if 525 00:45:41,240 --> 00:45:46,309 possible you want dust because you want a homogeneous bottle of dust you take a 526 00:45:46,309 --> 00:45:50,210 small portion of that and put it in a volumetric as a ten milliliter 527 00:45:50,210 --> 00:45:55,609 volumetric so now you've got so much weight you add to that THF you make a 528 00:45:55,609 --> 00:46:01,849 solution now so now you have a solution a THF solution of your sample the method 529 00:46:01,849 --> 00:46:05,960 calls for taking ten microliters of that put it in a small cup and evaporating a 530 00:46:05,960 --> 00:46:09,859 solvent such that you win with a very thin film of the sample on the inside 531 00:46:09,859 --> 00:46:14,240 surface of the cup at the bottom so to prepare a sample like this once the 532 00:46:14,240 --> 00:46:17,720 crowd millings been done to prepare a sample like this takes on the order of 533 00:46:17,720 --> 00:46:21,290 five minutes they only solve what you're going to use 534 00:46:21,290 --> 00:46:25,700 as 10 milliliters of the THF you're going to use disposable glassware so 535 00:46:25,700 --> 00:46:29,660 there's no worry about contamination or cross-contamination that little cup then 536 00:46:29,660 --> 00:46:34,040 is ready to be analyzed now if you wanted to do a screening method it's not 537 00:46:34,040 --> 00:46:37,579 necessary to go through the thin film process and that is you can take this 538 00:46:37,579 --> 00:46:41,990 sample dust from your jar and just weigh in a hundred micrograms or 200 539 00:46:41,990 --> 00:46:46,520 micrograms and put it directly in the cup so you analyze it as a solid if 540 00:46:46,520 --> 00:46:49,250 you'd like that internal standard at that point right now just a monitor 541 00:46:49,250 --> 00:46:53,150 performance that's easily done so either way you end up with the cup that's ready 542 00:46:53,150 --> 00:46:57,349 to analyze now the difference between a thin film that just making a THF 543 00:46:57,349 --> 00:47:02,240 solution put it on the cup and then evaporating the solvent and using the 544 00:47:02,240 --> 00:47:07,609 solid material is basically reflected in the precision so if I use a THF solution 545 00:47:07,609 --> 00:47:13,309 this is a half a milligram of sample now you can see for this de HB the percent 546 00:47:13,309 --> 00:47:18,500 relative standard deviation is about one percent for injections if I use the 547 00:47:18,500 --> 00:47:22,369 solid form for a screening method where I just take the dust if you will five 548 00:47:22,369 --> 00:47:26,240 point five milligrams of dust to put in the cup and analyze it directly you can 549 00:47:26,240 --> 00:47:30,799 see my precision goes down and of course the reason for that is is if I look at 550 00:47:30,799 --> 00:47:35,240 this this collections best that I have the chances of having the same amount of 551 00:47:35,240 --> 00:47:40,040 particles in each sample remote so I give it a more scatter than the data 552 00:47:40,040 --> 00:47:44,119 where if I make up a solution I can analyze that same solution numerous 553 00:47:44,119 --> 00:47:48,590 times and get exactly the same but for a screening technique that the 554 00:47:48,590 --> 00:47:53,990 solid analysis seems to work just fine can we hope to the end here thank you 555 00:47:53,990 --> 00:47:59,930 so a sample assistant a little cup this is on top of a liner - maple injection I 556 00:47:59,930 --> 00:48:05,450 dropped the cup in the furnace the furnace is at 100 degrees I hate the 557 00:48:05,450 --> 00:48:11,630 furnace 200 320 degrees and as I heat it up the phthalates will evolve and those 558 00:48:11,630 --> 00:48:15,950 are carried on to the column these little cups are can replace a lot of 559 00:48:15,950 --> 00:48:20,420 stuff but I can do a number of samples now one sample per hour the reason for 560 00:48:20,420 --> 00:48:23,750 that is is because the calibration the quantitation is done by a standard 561 00:48:23,750 --> 00:48:29,030 addition that requires two analysis one of the sample and one of the samples has 562 00:48:29,030 --> 00:48:34,400 been spiked with a known amount so that's to analysis so by about one an 563 00:48:34,400 --> 00:48:38,570 hour if you're going to do a screening sample that means one I don't have to 564 00:48:38,570 --> 00:48:42,110 program from one two three twenty I just drop it into three twenty so I don't 565 00:48:42,110 --> 00:48:46,100 have that 11 minute to feel real sample prep for extraction simple and then I 566 00:48:46,100 --> 00:48:52,180 could do about three per hour in the screening mode so the sample is heated I 567 00:48:52,180 --> 00:48:56,450 thermally extract the phthalates of interest they go on to the column and I 568 00:48:56,450 --> 00:49:02,510 get my chromatogram the conditions I'm using for my survey motor basically 100 569 00:49:02,510 --> 00:49:08,570 to 700 at a fairly high rate that could allow me to profile a characterize the 570 00:49:08,570 --> 00:49:12,080 sample and it tells me where the phthalates come in the temperature zone 571 00:49:12,080 --> 00:49:15,770 of which the phthalates evolve and then I do my thermal desorption my thermal 572 00:49:15,770 --> 00:49:21,710 desorption basically is 100 to 320 at 20 degrees a minute if you use in a thin 573 00:49:21,710 --> 00:49:25,250 film you can do it 40 degrees a minute rigea moment much difference this goes 574 00:49:25,250 --> 00:49:31,430 on to a column at 80 degrees so here's what it looks like the top traces by 575 00:49:31,430 --> 00:49:35,630 screen I don't have to do the screening for every sample the importance of the 576 00:49:35,630 --> 00:49:40,100 screen is it characterizes the sample if I'm doing PVCs forever I only have to do 577 00:49:40,100 --> 00:49:43,970 this once if I'm doing polypropylene I only have to do it once but if I'm doing 578 00:49:43,970 --> 00:49:48,950 circuit boards or if I'm doing different kinds of materials then maybe I have to 579 00:49:48,950 --> 00:49:53,930 do my screen to find out where my if my phthalates have shifted but you can see 580 00:49:53,930 --> 00:49:58,970 if I'm the top trace this is this a PVC sampled inch as a plasticizer I get a 581 00:49:58,970 --> 00:50:01,820 large group of compounds out fester phthalates any 582 00:50:01,820 --> 00:50:06,040 dents may be present there's also a peak for HCl because that's the decomposition 583 00:50:06,040 --> 00:50:11,450 product of polyvinyl chloride and then of course I get my fractions out there 584 00:50:11,450 --> 00:50:18,980 right polymerized or I realize the PVC so I find my zone by looking at ions and 585 00:50:18,980 --> 00:50:22,790 you can see the lower trace where it says phthalates 149 you can see all the 586 00:50:22,790 --> 00:50:28,970 149 all my phthalates are out by 320 and so my thermal desorption zone is 100 to 587 00:50:28,970 --> 00:50:33,440 320 at 20 degrees a minute it's a nice thing about this is by doing this I'm 588 00:50:33,440 --> 00:50:36,950 going to extract those phthalates and put those on the columns for separation 589 00:50:36,950 --> 00:50:42,910 but I leave behind in the cup all the polymer so I don't have to worry about 590 00:50:42,910 --> 00:50:47,600 faking the pulp making the system system at the cleanup the polymer I don't have 591 00:50:47,600 --> 00:50:51,680 to worry about contamination of my system as I backflash or for the polymer 592 00:50:51,680 --> 00:50:54,770 just stays in the cup of when I'm done I watched a polymer out and reuse the cup 593 00:50:54,770 --> 00:51:00,020 or get a new cup all I'm going to inject under the GC is just that fracks of a 594 00:51:00,020 --> 00:51:04,570 sample that's extracted at 320 degrees 595 00:51:04,900 --> 00:51:09,920 so I can identify different compounds by ions this right here again this is just 596 00:51:09,920 --> 00:51:13,640 your standard this is probably more interesting right here this is the 597 00:51:13,640 --> 00:51:18,290 reproducibility this is 6 injections of a PVC dense sample and it's a little 598 00:51:18,290 --> 00:51:22,370 hard to read but what I have here is this percent relative standard deviation 599 00:51:22,370 --> 00:51:27,560 of the precision of a multiple runs of the same sample and you can see the 600 00:51:27,560 --> 00:51:33,560 precision across the board is less than less than 2% so I can take one solution 601 00:51:33,560 --> 00:51:38,530 and analyze the six times and my precision is pretty darn good 602 00:51:39,460 --> 00:51:43,220 remember I mentioned that this is a standard addition method so I'm going to 603 00:51:43,220 --> 00:51:47,690 run my sample and get an area number for my compound and then I'm going to spike 604 00:51:47,690 --> 00:51:51,730 the sample with a known amount in this case point one five percent 605 00:51:51,730 --> 00:51:57,200 concentration and going to rerun the sample so this is just the spiked sample 606 00:51:57,200 --> 00:52:00,830 I just show three of these right here so this is the PVC dense sample where 607 00:52:00,830 --> 00:52:04,910 that's been spiked with a known amount of each of the phthalates and again you 608 00:52:04,910 --> 00:52:09,430 can see the precision across the bottom of the spiked numbers again less than 2% 609 00:52:09,430 --> 00:52:14,150 so it's very precise I end up with a series of curves like 610 00:52:14,150 --> 00:52:19,400 this so these are the six calibration curves for the six compounds the one in 611 00:52:19,400 --> 00:52:23,870 the middle is that the zero that's the sample number the one on the far right 612 00:52:23,870 --> 00:52:28,010 that's the spike number and there's a meth Max or go through and I can 613 00:52:28,010 --> 00:52:34,850 calculate the amount of amount of pieces of phthalates in the original sample and 614 00:52:34,850 --> 00:52:39,200 if you do that again you can see the precision there is less than 2% and it's 615 00:52:39,200 --> 00:52:43,940 a little hard to read but the numbers the concentration of this of each tally 616 00:52:43,940 --> 00:52:49,670 that this particular one was about 980 990 nanograms so the accuracy is pretty 617 00:52:49,670 --> 00:52:54,830 good now that you see it korea is also interested in this method this is some 618 00:52:54,830 --> 00:52:58,250 of their work these are their six calibration curves only in this case 619 00:52:58,250 --> 00:53:01,820 they spiked with three mount three different levels and all you do is take 620 00:53:01,820 --> 00:53:05,660 that one solution and you can see from your upper right trace one case you put 621 00:53:05,660 --> 00:53:08,780 two microliters the next case three microliters the next case 5 microliters 622 00:53:08,780 --> 00:53:12,650 x8 merica there's that's how you get you multiple points so it's still one 623 00:53:12,650 --> 00:53:17,150 solution and you can see their recoveries are of all the six phthalates 624 00:53:17,150 --> 00:53:22,490 are pretty good and their precision is also less than one one percent in this 625 00:53:22,490 --> 00:53:27,170 case now we didn't mess the salvation study that is we've been out to found 626 00:53:27,170 --> 00:53:30,140 five laboratories who are willing to try this these as laboratories that hadn't 627 00:53:30,140 --> 00:53:34,850 done this before in one case one of the laboratories had a new higher to that to 628 00:53:34,850 --> 00:53:39,230 the study force and this is this is what we found from the validation study 629 00:53:39,230 --> 00:53:44,090 I sent them four samples to them with the same sample the thermal desorption 630 00:53:44,090 --> 00:53:49,340 temperature system dependent by that I mean if you have a factory system or a 631 00:53:49,340 --> 00:53:55,040 Pvt in the system or a CVS system or a Gerstel system whatever system you're 632 00:53:55,040 --> 00:53:59,240 using for your thermal desorption you have to be very sure that what you're 633 00:53:59,240 --> 00:54:03,830 looking at is the sample temperature or not the thermocouple temperature so 634 00:54:03,830 --> 00:54:06,800 there's some differences in some systems between the set point and the actual 635 00:54:06,800 --> 00:54:10,730 point how you ready to do is run the the EGA and you can determine the 636 00:54:10,730 --> 00:54:15,320 temperature range of a which that system operates best some of the validation 637 00:54:15,320 --> 00:54:20,810 labs you sim some of the validation labs you scan it both to produce comparable 638 00:54:20,810 --> 00:54:25,310 data thin photo columns are definitely preferred over thick film columns we 639 00:54:25,310 --> 00:54:27,090 don't a lot of retention and a whole lot of 640 00:54:27,090 --> 00:54:30,480 time in there the standard edition everyone use standard edition at one 641 00:54:30,480 --> 00:54:34,980 point standard edition the r-squared was always greater than 0.99 if you if you 642 00:54:34,980 --> 00:54:38,520 recalled back to this study this is this is three points plus the sample in the R 643 00:54:38,520 --> 00:54:43,260 squares and all these are one but these five laboratories all data point nine 644 00:54:43,260 --> 00:54:47,340 nine are better the inner lab injection to Jackson reproducibility is less than 645 00:54:47,340 --> 00:54:51,450 five percent the data I've shown here is all about two percent one of my five 646 00:54:51,450 --> 00:54:56,400 labs with the newbie they were they were about thirty percent higher than 647 00:54:56,400 --> 00:54:59,700 everybody else in the whole wide world so there was some systematic issue there 648 00:54:59,700 --> 00:55:03,990 but I included all their data that's how it comes out to be five percent the 649 00:55:03,990 --> 00:55:08,070 inter lab sample the sample reproducibility is always less than ten 650 00:55:08,070 --> 00:55:13,380 percent and the laboratory laboratory accuracy is 25 percent now get if I take 651 00:55:13,380 --> 00:55:17,460 out the data from that one lab and drop down to about ten percent but I can't 652 00:55:17,460 --> 00:55:20,880 find a reason to do that so these are the numbers we came up with from the 653 00:55:20,880 --> 00:55:26,310 validation study of these five laboratories now all of a sudden we're 654 00:55:26,310 --> 00:55:28,950 getting requests for an extended target compound list so here's the extended 655 00:55:28,950 --> 00:55:32,820 target compound this we've been asked to look at next is this method I've 656 00:55:32,820 --> 00:55:36,810 highlighted in red the six compounds we started with in order to do this 657 00:55:36,810 --> 00:55:39,300 chromatic graphically it's a simple thing he just dropped the initial 658 00:55:39,300 --> 00:55:42,720 temperature from 100 to 80 degrees and he tried to do a little bit better 659 00:55:42,720 --> 00:55:47,370 separation on that front end better stow your host that only goes up to D ID P so 660 00:55:47,370 --> 00:55:50,730 it doesn't go any further so the analysis time is still on the order of 661 00:55:50,730 --> 00:55:54,660 about twenty minutes so it has already lengthen your analysis time and since 662 00:55:54,660 --> 00:55:58,650 your sample prep time is baking up a ten microliters 10 milliliter solution of 663 00:55:58,650 --> 00:56:01,890 THF it's it doesn't affect any of your sample prep and your operational 664 00:56:01,890 --> 00:56:07,470 parameters so it looks that was like it's almost too good to be true we've 665 00:56:07,470 --> 00:56:14,100 done this for three years the TD method is easy it takes one syringe and a 666 00:56:14,100 --> 00:56:17,130 little bit of glassware it's clean there's no cleaning the cleaning and 667 00:56:17,130 --> 00:56:20,550 cleaning and cleaning and socks with extractors that sort of thing it's great 668 00:56:20,550 --> 00:56:25,290 because I'm using almost no solvent at all and it's fully automated that sounds 669 00:56:25,290 --> 00:56:28,380 really really good it's precise and accurate the precision is always less 670 00:56:28,380 --> 00:56:33,120 than 2% the accuracy is plus or minus 10% in your laboratory and it 671 00:56:33,120 --> 00:56:37,200 accommodates an extended come down list so this is all well and good there is a 672 00:56:37,200 --> 00:56:41,400 downside though the downside is this run to run 673 00:56:41,400 --> 00:56:48,329 contamination issue was a real problem the and thousand for millions that not 674 00:56:48,329 --> 00:56:53,219 too much of an issue that's bucket chemistry but as the as the detection as 675 00:56:53,219 --> 00:56:57,779 the sensitivity requirements get higher and higher more and more sensitivity we 676 00:56:57,779 --> 00:57:01,289 have to wait find a way to really monitor this contamination the 677 00:57:01,289 --> 00:57:04,019 contamination is in the injection port there's no doubt about it 678 00:57:04,019 --> 00:57:09,239 also the quantiles would have to be verified as we change matrices that's 679 00:57:09,239 --> 00:57:13,380 one thing to look at PVC which is what the ASTM method was focused on and we 680 00:57:13,380 --> 00:57:16,109 know appropriate probably propylene and probably either ethylene and we've done 681 00:57:16,109 --> 00:57:18,900 a number of different polymers what happens with the circuit board what 682 00:57:18,900 --> 00:57:21,960 happens with it some kind of material you haven't really looked at so you 683 00:57:21,960 --> 00:57:25,589 really have to verify that you have no in no interference when you start 684 00:57:25,589 --> 00:57:29,219 changing matrices and the second the third thing is when you deal with these 685 00:57:29,219 --> 00:57:34,619 compounds that are isomeric mixtures like di DP the quantitation becomes a 686 00:57:34,619 --> 00:57:38,249 little bit more difficult it could be I love my mother would kill me for saying 687 00:57:38,249 --> 00:57:42,509 this it could be HPLC may be a better way to do these multiple these compounds 688 00:57:42,509 --> 00:57:46,170 that have a lot of different isomers so in the end those of us that develop 689 00:57:46,170 --> 00:57:49,920 methods are in the deep trouble here because now we've got them we've got a 690 00:57:49,920 --> 00:57:54,479 method now that was developed for six compounds in PVC and we're asked to do 691 00:57:54,479 --> 00:57:58,319 more and more phthalates and we're asked to do it more and more different 692 00:57:58,319 --> 00:58:03,359 matrices remember being asked get lower and lower and higher 693 00:58:03,359 --> 00:58:07,499 I guess higher and higher sensitivity and in the case of phthalates this could 694 00:58:07,499 --> 00:58:12,960 be a real challenge for the laboratory any questions we have time for one or 695 00:58:12,960 --> 00:58:17,930 two questions yes 696 00:58:19,069 --> 00:58:28,640 that was our SD company yeah yeah that's what a half safer yes 697 00:58:36,510 --> 00:58:41,349 yeah the question is is the precision accuracy depended upon of the cryogenic 698 00:58:41,349 --> 00:58:47,920 billing of a sample all the work here was done with PVC standards that were 699 00:58:47,920 --> 00:58:52,630 prepared by one of the members of the ASTM committee and so it wasn't 700 00:58:52,630 --> 00:59:15,910 literally a sheet of PVC and so yes see now you're getting into legal issues 701 00:59:15,910 --> 00:59:19,599 yeah I mean obviously you are as a citizen I think you are but as the the 702 00:59:19,599 --> 00:59:24,089 methodology that we've familiar with it calls for a number for the entire 703 00:59:24,089 --> 00:59:29,109 product and so yes you are diluting the beak but on the on the other end you 704 00:59:29,109 --> 00:59:34,690 know how much the because of the duct you know what but that's the critical 705 00:59:34,690 --> 00:59:38,640 issues at homogeneity sample homogeneity 706 00:59:40,890 --> 00:59:47,650 just quickly to add on to that that we're really not here to talk about the 707 00:59:47,650 --> 00:59:54,910 policy and the regulations but we have issued guidance that it's the component 708 00:59:54,910 --> 01:00:02,829 parts that the thallus limit applies to so we're our very initial guidance was 709 01:00:02,829 --> 01:00:11,950 different based on the initial read of the rule we have guided the individual 710 01:00:11,950 --> 01:00:19,270 component parts but regardless of that then the analysis is still the same all 711 01:00:19,270 --> 01:00:21,390 right 712 01:00:25,349 --> 01:00:30,750 up next we have chrissteele from bureau veritas 713 01:00:38,700 --> 01:00:42,839 you could just press forward or back or you can press one of these buttons 714 01:00:42,839 --> 01:00:49,059 doesn't make sure you speak clear enough came back alright thanks Matt yes I'm 715 01:00:49,059 --> 01:00:53,829 filling in for Lisa Clarissa a global technical consultant specialist because 716 01:00:53,829 --> 01:00:58,599 she is there's a touch of a flu bug going spreading around at our Buffalo 717 01:00:58,599 --> 01:01:03,460 office so hopefully I don't get it after after we leave to get back to Buffalo 718 01:01:03,460 --> 01:01:12,150 but so I'm speaking on behalf of Jarrow Veritas in lieu of her so yes no problem 719 01:01:12,150 --> 01:01:18,160 so thank you Matt for letting me represent our company here and I'm here 720 01:01:18,160 --> 01:01:22,839 today to talk about using a dual instrumentation for phthalates analysis 721 01:01:22,839 --> 01:01:29,559 and plastics and what I mean by that is two systems to mass spectrometers the 722 01:01:29,559 --> 01:01:33,430 first of course GCMs has I think a lot of you are familiar with and that the 723 01:01:33,430 --> 01:01:39,579 CPSC method revolves around but secondly the lc-ms system using both in 724 01:01:39,579 --> 01:01:47,589 conjunction with each other just to kind of rule out any interferences that GCMs 725 01:01:47,589 --> 01:01:52,680 may pose basically to get like a second set of eyes looking at a particular 726 01:01:52,680 --> 01:01:58,630 sample scan bureau veritas his head about I'm guessing at least 10 years of 727 01:01:58,630 --> 01:02:02,829 experience testing for phthalates in a variety of consumer products many 728 01:02:02,829 --> 01:02:08,859 different plastics and I'm here to try to share with you hopefully some help 729 01:02:08,859 --> 01:02:13,359 for helpful information that has worked for us in our testing approach to 730 01:02:13,359 --> 01:02:18,819 resolve these tricky samples as we know as time goes on and regulations are 731 01:02:18,819 --> 01:02:23,470 expanding manufacturers seem to be trying to get more and more clever as 732 01:02:23,470 --> 01:02:29,770 trying to find workarounds to find alternatives plasticizer alternatives to 733 01:02:29,770 --> 01:02:36,069 have their samples compliance so in effect you're going to we see it we see 734 01:02:36,069 --> 01:02:40,869 a lot of different scans and our thalut extracts because of this because they're 735 01:02:40,869 --> 01:02:43,230 using 736 01:02:43,289 --> 01:02:51,400 alternatives sure sure sorry so that's that's my purpose here today is to try 737 01:02:51,400 --> 01:02:59,260 to share with you our daily testing approach so just as a quick outline I'm 738 01:02:59,260 --> 01:03:05,890 gonna go over the test method that we use the instrumentation that we use GCMs 739 01:03:05,890 --> 01:03:12,880 and LCS LCMS of course results in interpretation and I'll answer try to 740 01:03:12,880 --> 01:03:21,670 answer any questions you may have about our approach our test method extremely 741 01:03:21,670 --> 01:03:28,960 similar to what's in CPSC essentially we cut the sample into very small pieces of 742 01:03:28,960 --> 01:03:34,140 the component we place it to a disposable glass reaction vessel or vial 743 01:03:34,140 --> 01:03:42,099 then we add tetrahydrofuran THF and sonicated at 40 degrees centigrade for 744 01:03:42,099 --> 01:03:47,079 30 minutes which in most cases will be long enough and aggressive enough to get 745 01:03:47,079 --> 01:03:52,359 that into the organic solution in Sonic 8 an additional 30 minutes if that 746 01:03:52,359 --> 01:03:56,349 sample does not visibly dissolve sometimes that happens with harder 747 01:03:56,349 --> 01:04:05,470 plastics after which acetyl nitrile is what we use acetyl nitrile ACN is that a 748 01:04:05,470 --> 01:04:13,059 drop ice to precipitate off the polymer that's been very useful for us I know 749 01:04:13,059 --> 01:04:18,069 other solvents and the CBC mentions hexane using hexane 750 01:04:18,069 --> 01:04:24,849 other LEDs may be using methanol they may work in particular applications or 751 01:04:24,849 --> 01:04:32,109 plastics PVC probably works but we've found that co nitrile will precipitate 752 01:04:32,109 --> 01:04:39,609 out more polymer more types of polymers than the other solvents so in in the end 753 01:04:39,609 --> 01:04:47,829 it results in a cleaner layer on top of your precipitated plasticizer a very 754 01:04:47,829 --> 01:04:53,740 precipitated polymer so you're all that junk and interfering things that may 755 01:04:53,740 --> 01:04:57,769 interfere what the analysis will come out of that solution and then you can 756 01:04:57,769 --> 01:05:06,529 inject a much more clean solution into your instrument so once that is done 757 01:05:06,529 --> 01:05:14,089 you'll have to stand for 30 minutes and take that solution and to put it into an 758 01:05:14,089 --> 01:05:20,029 autosampler vial and it's ready for analysis actually ad if they're seeing 759 01:05:20,029 --> 01:05:24,829 good rate of the unforeseen there's an internal standard then you can filter it 760 01:05:24,829 --> 01:05:36,579 and analyze it by GCMs indoor lcms and currently LCMS is not listed in the cps 761 01:05:36,579 --> 01:05:45,109 c method currently I will go most of you probably are already aware of the 762 01:05:45,109 --> 01:05:51,199 function of gas chromatography you have a carrier gas usually helium the sample 763 01:05:51,199 --> 01:05:57,529 is injected in the injector volatilized goes to the column the analyte separate 764 01:05:57,529 --> 01:06:01,789 out from one another as well as any interfering compounds they separate out 765 01:06:01,789 --> 01:06:06,739 from one another then it enters the mass spec detector fragmentation occurs a 766 01:06:06,739 --> 01:06:15,559 mass spectrum is produced and the signal is plotted on the chromatogram okay what 767 01:06:15,559 --> 01:06:19,669 we're looking at here is just an example of many different types of phthalates 768 01:06:19,669 --> 01:06:24,769 that are out there obviously it's not a complete list but it's just it's just 769 01:06:24,769 --> 01:06:29,049 here to demonstrate what we could potentially be looking at when we 770 01:06:29,049 --> 01:06:35,929 analyze a particular sample extract any one of these or a combination of these 771 01:06:35,929 --> 01:06:42,799 could be found in your sample so a lot of them are nice clean needle peaks of 772 01:06:42,799 --> 01:06:46,909 course as mad as mention and many of you already know we have the broad finger 773 01:06:46,909 --> 01:06:53,989 peak type sale lights to that a regulated di MPD IDP you can't see it 774 01:06:53,989 --> 01:06:58,339 too much on this slide but you know it's it's buried in there between the 12 and 775 01:06:58,339 --> 01:07:04,669 13 minute range so this is just to demonstrate what we could be looking at 776 01:07:04,669 --> 01:07:07,460 in a sample and like I said this is not a complete with 777 01:07:07,460 --> 01:07:18,320 by any means some of these are regulated some are not so go on to our next slide 778 01:07:18,320 --> 01:07:26,180 this is just an example of a mass spectrum of DBP just as an example we go 779 01:07:26,180 --> 01:07:31,220 back a slide DBP is just one that's highlighted as an example if we look at 780 01:07:31,220 --> 01:07:36,050 the mass spectrum creating that response this is it 781 01:07:36,050 --> 01:07:44,630 of course they speak 149 is very common qualifying ion could be 223 which is 782 01:07:44,630 --> 01:07:53,390 unique to DBP now a GC mass spectrum of di NPD IDP those troublesome finger 783 01:07:53,390 --> 01:08:00,500 peaks you could the InP would be 293 you could extract that out of the 784 01:08:00,500 --> 01:08:05,480 chromatogram but even doing so it still can sometimes be a challenge depending 785 01:08:05,480 --> 01:08:09,800 on what what you might have interfering with that I'm going to talk a little bit 786 01:08:09,800 --> 01:08:17,540 more about that in the upcoming slides as well this is an example of a non 787 01:08:17,540 --> 01:08:22,520 regulated daylight currently unregulated you never know what the future holds dye 788 01:08:22,520 --> 01:08:28,640 ISO octal phthalates basically this is a finger peak as well this may be present 789 01:08:28,640 --> 01:08:32,509 a sample you don't know what manufacturers are putting in we've 790 01:08:32,509 --> 01:08:38,270 certainly seen it many times before in samples dye ISO octal phthalates it's a 791 01:08:38,270 --> 01:08:43,580 it's like a couple covered carbon chains last of course then Diet di n P and D 792 01:08:43,580 --> 01:08:49,790 IDP the nanos and decals so here you can see their retention time it's a range 793 01:08:49,790 --> 01:08:56,630 it's a broad range it's it's in isomeric mix of course and that's why it looks 794 01:08:56,630 --> 01:09:02,029 the way it does so you can see it spans across the time line retention time line 795 01:09:02,029 --> 01:09:09,290 you know between like eleven point two five minutes to twelve and a half so is 796 01:09:09,290 --> 01:09:14,270 if you see something like this in a sample it can be challenging to properly 797 01:09:14,270 --> 01:09:20,540 integrate the regulated phthalates or even see if they're there di NPD IDP 798 01:09:20,540 --> 01:09:25,520 even after ion extraction honing in on a particular ion that may be unique to 799 01:09:25,520 --> 01:09:41,170 that particular Valley so here is an example of di MP on a GC chromatogram 800 01:09:41,170 --> 01:09:46,460 highlighted there it's it's if you want to call that in a pax it's peeking out 801 01:09:46,460 --> 01:09:51,350 around 13 minutes but the range of isomers begins at about 12 and a half 802 01:09:51,350 --> 01:09:58,520 and extends out to like 13 and a half minutes so anyone doing a lead analysis 803 01:09:58,520 --> 01:10:05,410 by GC this is second nature I'm sure see this all the time so again it's very 804 01:10:05,410 --> 01:10:12,080 difficult to integrate and try to accurately capture the area counts of 805 01:10:12,080 --> 01:10:21,170 that di e MP peak if you have other interferences or other phalates present 806 01:10:21,170 --> 01:10:26,170 it just it can be challenging on the GC 807 01:10:31,500 --> 01:10:36,780 so here we're just looking at some chemical structures of some regulated 808 01:10:36,780 --> 01:10:44,250 thelet's we have d NOP di n p di DP d NOP is unbranched so that's it it's a 809 01:10:44,250 --> 01:10:53,100 single peak but all three of these have roughly the same retention time on GC D 810 01:10:53,100 --> 01:10:58,920 NOP is an octal di o P which I mentioned before is an ISO octal so you're going 811 01:10:58,920 --> 01:11:04,740 to see 279 ion 279 even if you extract enough for DN o P if you have di o P in 812 01:11:04,740 --> 01:11:10,680 your sample and what do you do you see this big under al unregulated 279 I in 813 01:11:10,680 --> 01:11:16,080 chromatogram and then you may or may not see this little peak come out of da that 814 01:11:16,080 --> 01:11:21,030 may or may not be DN o P if it is DN o P and you're confident it is okay now how 815 01:11:21,030 --> 01:11:24,900 do you quantico annotate it it's very hard to baseline integrate when it's 816 01:11:24,900 --> 01:11:34,320 coming out of a mess so di NP + di D P of course our isomeric 817 01:11:34,320 --> 01:11:41,790 finger Peaks they actually overlap on GC even though they have quantifying their 818 01:11:41,790 --> 01:11:48,210 qualifying ions associated with them they can be troublesome as well and of 819 01:11:48,210 --> 01:11:54,450 course the reason that they are broad finger peaks is because I so know no di 820 01:11:54,450 --> 01:12:03,350 NP and I sewed a co di DP have it could be a multiple of arrangements of the 821 01:12:03,350 --> 01:12:08,640 groups on methyl groups they could be located in many different statistical 822 01:12:08,640 --> 01:12:13,110 possibility and that's why you see that broad finger peak of course it's not 823 01:12:13,110 --> 01:12:17,340 just a single analyte it's a mixture of isomers I'm sure you're all familiar 824 01:12:17,340 --> 01:12:22,130 with why they look the way they do on GC 825 01:12:22,190 --> 01:12:27,540 now let's get into lcms instrumentation liquid 826 01:12:27,540 --> 01:12:33,210 chromatography coupled with a mass spectrometer pretty much basically the 827 01:12:33,210 --> 01:12:38,550 same principles GCMs you're just using liquid is the mobile phase or carrier to 828 01:12:38,550 --> 01:12:45,070 carry along your analytes they get separated by a column the same 829 01:12:45,070 --> 01:12:52,000 renters spray chamber mobile phases evaporated fragmentation occurs and then 830 01:12:52,000 --> 01:12:58,230 the resulting ions are separated out by mass to charge ratio and response is 831 01:12:58,230 --> 01:13:09,130 created as well as a spectrum so this is an example this is a di NP at 1 ppm on 832 01:13:09,130 --> 01:13:16,270 the LCMS so what we're looking at here is we run in scan mode this is actually 833 01:13:16,270 --> 01:13:23,199 I in 419 I believe di NP and this is only 1 ppm we do run standards a little 834 01:13:23,199 --> 01:13:29,050 bit lower than this but the point is you can see how much better it looks to a 835 01:13:29,050 --> 01:13:33,520 chemist I mean this this I like the way it looks it's very integrated the 836 01:13:33,520 --> 01:13:42,460 signal-to-noise ratio is very large it's just just a great responding signal for 837 01:13:42,460 --> 01:13:47,679 VI NP it just jumps out of the baseline is it's it's great 838 01:13:47,679 --> 01:13:57,329 di DP at 1 ppm similar similar look to it comes right out of the baseline you 839 01:13:57,329 --> 01:14:02,440 know you get a much better response of course than compared to GC there's no 840 01:14:02,440 --> 01:14:10,409 broad finger peaks and actually the IDP is fully resolved from di n p on the 841 01:14:10,409 --> 01:14:17,130 lc-ms I'm sorry 842 01:14:17,460 --> 01:14:28,170 yeah it's reverse phased yep and and this slide is just kind of giving you a 843 01:14:28,170 --> 01:14:34,950 side-by-side a di NP in the upper right on the lc/ms di NP and the lower left 844 01:14:34,950 --> 01:14:43,290 and the GCMs that you can see it's hard to see of course because di NP n GCMs 845 01:14:43,290 --> 01:14:50,160 relative to the single analytes it just kind of it's not very responsive because 846 01:14:50,160 --> 01:14:56,940 it's just a nice American mix so that's one advantage that we found with using 847 01:14:56,940 --> 01:15:08,310 lc-ms is really for for those finger peaks so our approach like I said we use 848 01:15:08,310 --> 01:15:15,300 both GCMs and lc-ms in conjunction with one another if the lab decides to use 849 01:15:15,300 --> 01:15:21,510 GCMs primarily it's kind of a flow chart showing what should be done if you find 850 01:15:21,510 --> 01:15:29,400 the family's DN o pd ID PDI NP they should be confirmed on lc-ms just just 851 01:15:29,400 --> 01:15:36,300 to ensure a good quantitation and just to confirm that's out there now if 852 01:15:36,300 --> 01:15:43,980 you're going to primarily use LCMS you can do that as well but then yet there's 853 01:15:43,980 --> 01:15:48,360 things you need to know about that though if you find DB p dibutyl 854 01:15:48,360 --> 01:15:54,090 phthalate which is regulated it also that well it will call a loop with an 855 01:15:54,090 --> 01:15:59,480 unregulated thell a die isobutyl thely so if you're getting a detection on DB p 856 01:15:59,480 --> 01:16:05,940 it may really be die isobutyl faily they they essentially Khoa loot with one 857 01:16:05,940 --> 01:16:13,440 another so that's why if you do find DB p it's it's pretty recommended pretty 858 01:16:13,440 --> 01:16:17,790 urgent that you confirm it by GCMs to see is it the regulated form of the 859 01:16:17,790 --> 01:16:26,160 unregulated or a mixture of both and we've seen all three cases there so that 860 01:16:26,160 --> 01:16:32,110 that's pretty much the flow that that we found to work for us 861 01:16:33,560 --> 01:16:39,350 so in conclusion a dual instrument system works for us it's been a useful 862 01:16:39,350 --> 01:16:44,960 approach enhancing our data integrity with challenging samples and like I said 863 01:16:44,960 --> 01:16:51,230 before as time goes on we just just when you think you've seen it all you haven't 864 01:16:51,230 --> 01:16:56,510 we've seen new plastic plastics come out with different compounds and adding new 865 01:16:56,510 --> 01:17:04,040 challenges it's like an ongoing process the learning never ends so this is what 866 01:17:04,040 --> 01:17:07,580 Bureau of our Bureau Bureau Veritas has found to work for us in our long history 867 01:17:07,580 --> 01:17:12,770 of fail a testing in order to provide clear results from an otherwise messy 868 01:17:12,770 --> 01:17:18,050 scan just because of this we feel much more confident and the data that we 869 01:17:18,050 --> 01:17:23,800 issue basically we were having two detectors give us data if need be 870 01:17:23,800 --> 01:17:30,110 it's also important to note that you don't need a state-of-the-art gc-ms or 871 01:17:30,110 --> 01:17:35,810 lc/ms I mean you can use models that been around for years it's not like you 872 01:17:35,810 --> 01:17:39,740 have to go out and buy the the most sensitive instrument to take this 873 01:17:39,740 --> 01:17:44,870 approach on so that in that sense it helps labs that I'm looking for you know 874 01:17:44,870 --> 01:17:51,320 cost savings of course so in the end it's all about just feeling confident 875 01:17:51,320 --> 01:17:58,160 about the results and data that your lab is issuing with these tricky samples are 876 01:17:58,160 --> 01:18:03,910 there any questions yes 877 01:18:10,400 --> 01:18:17,610 yes the question was do our labs in Asia used the dual method approach I'm not 878 01:18:17,610 --> 01:18:21,420 sure I from my understanding I know they they have both okay 879 01:18:21,420 --> 01:18:26,670 my consultant they're saying yes they do I knew they had both instrumentations 880 01:18:26,670 --> 01:18:31,010 but I just got confirmation that yes they do 881 01:18:39,969 --> 01:18:46,360 the question was is this our standard practice in testing for di MP & di DP 882 01:18:46,360 --> 01:18:50,499 yes it is yeah just because it's just so tricky on 883 01:18:50,499 --> 01:18:55,239 GCMs we wouldn't just we just wouldn't feel that confident issuing results if 884 01:18:55,239 --> 01:18:58,989 we get something that would really challenge the chromatography like we 885 01:18:58,989 --> 01:19:06,939 often see on GCMs so yeah this this is our our good practice here bébé yep go 886 01:19:06,939 --> 01:19:09,059 ahead 887 01:19:16,480 --> 01:19:25,670 on LCMS sure actually I can go back that's fine um actually if we overlaid 888 01:19:25,670 --> 01:19:30,830 them it show better but this is there are two separate identic stretches as 889 01:19:30,830 --> 01:19:36,350 well this is a leaf for tickets for 19 I'm the LCMS you want to take a look at 890 01:19:36,350 --> 01:19:42,080 this you know starting off it you know ten and a half going to twelve and here 891 01:19:42,080 --> 01:19:52,430 we got twelve - like 14 for di DPL CMS total run time including the post run 892 01:19:52,430 --> 01:19:58,900 and leave just 22 minutes something like that 24 minutes 893 01:20:08,410 --> 01:20:25,700 yeah yep okay yeah we're involved in internal correlations with their own 894 01:20:25,700 --> 01:20:29,600 company as well as external correlations to see if the methodologies that other 895 01:20:29,600 --> 01:20:33,410 labs are using are comparable with ours so yeah that's that's part of our 896 01:20:33,410 --> 01:20:41,080 quality control all right let's thank Chris thank you 897 01:20:42,380 --> 01:20:46,780 up next we have Luke Ackerman from the FDA 898 01:20:57,180 --> 01:21:05,290 thank you all for coming and thanks for organizing this okay okay so today I'm 899 01:21:05,290 --> 01:21:10,120 going to be discussing dart MS or direct analysis in real time which is an 900 01:21:10,120 --> 01:21:15,340 ambient ionization mass spectrometry technique as a possible screening method 901 01:21:15,340 --> 01:21:18,910 for phthalates specifically we've been doing a lot of work on food-contact 902 01:21:18,910 --> 01:21:25,239 polymers and looking for rapid screening techniques phthalates just happens to be 903 01:21:25,239 --> 01:21:31,260 one of the model additives that we look at whenever we evaluate methodology so I 904 01:21:31,260 --> 01:21:36,460 thought perhaps I could share a little bit of our work with you here and I 905 01:21:36,460 --> 01:21:40,510 think just to kind of give you the conclusion I think dart can be used as a 906 01:21:40,510 --> 01:21:46,060 very effective screening technique it has limited capabilities otherwise but 907 01:21:46,060 --> 01:21:50,410 I'll be going over the details of that and I work at the Center for Food Safety 908 01:21:50,410 --> 01:21:56,469 and applied nutrition at the FDA we're a research arm of the FDA so I'm not 909 01:21:56,469 --> 01:22:02,110 conducting any regulatory enforcement actions at our facility we're developing 910 01:22:02,110 --> 01:22:06,760 methodology and trying to advance the science at the agency so I won't be 911 01:22:06,760 --> 01:22:14,140 discussing any legal matters either so how does dart work well dart is as I 912 01:22:14,140 --> 01:22:19,180 said an ambient ionization technique it's just one commercial application of 913 01:22:19,180 --> 01:22:26,100 many different you've probably heard of desi dart a sap gosh what else nano desi 914 01:22:26,100 --> 01:22:32,110 supersonic electrospray ionisation these are all the academic terms for various 915 01:22:32,110 --> 01:22:38,050 techniques of producing gas phase ions off of condensed materials so solids and 916 01:22:38,050 --> 01:22:43,540 liquids and turning them into gas phase ions such that mass spectrometry can be 917 01:22:43,540 --> 01:22:48,910 used to help analyze the stuff in question in this particular case dart is 918 01:22:48,910 --> 01:22:52,930 unique and was probably granted a patent because it quenches a plasma it 919 01:22:52,930 --> 01:22:57,400 generates a plasma of helium in the glow discharge area of the diagram here and 920 01:22:57,400 --> 01:23:02,560 then it quenches them on the grounded electrodes in a further down stream it 921 01:23:02,560 --> 01:23:07,750 then subsequently heat it heats that gas and the quenched plasma generates 922 01:23:07,750 --> 01:23:12,820 excited helium or metastable helium which is just an electron shifted up in 923 01:23:12,820 --> 01:23:18,880 energy level in the orbitals of helium once you heat this helium stream you now 924 01:23:18,880 --> 01:23:23,649 have hot excited helium it exits the dart source and into the atmosphere of 925 01:23:23,649 --> 01:23:28,809 the lab where you place your sample the atmosphere in the lab not surprisingly 926 01:23:28,809 --> 01:23:35,499 contains water vapor and water has a good match with the energy of the 927 01:23:35,499 --> 01:23:40,510 excited helium and it produces protonated water clusters and these 928 01:23:40,510 --> 01:23:45,489 protonated water clusters in turn ionized any gas phase molecules in the 929 01:23:45,489 --> 01:23:51,219 vicinity of the source there's been lots of studies on how big of a gap you need 930 01:23:51,219 --> 01:23:56,019 and for different compounds different distances between the exit of the dart 931 01:23:56,019 --> 01:23:58,899 and the entrance of the mass spectrometer will yield better results 932 01:23:58,899 --> 01:24:04,119 but in general your protonating whatever gas phase ions you can get and the 933 01:24:04,119 --> 01:24:10,689 thermal heating of the helium gas also allows thermal transfer to the surfaces 934 01:24:10,689 --> 01:24:15,369 so you're doing thermal desorption so dart is thermal desorption atmospheric 935 01:24:15,369 --> 01:24:19,689 chemical ionization similar to the negative and positive chemical 936 01:24:19,689 --> 01:24:24,669 ionization possibilities with standard GCMs techniques but this is done in the 937 01:24:24,669 --> 01:24:28,899 open lab atmosphere and the advantage of that is that allows you to stick odd 938 01:24:28,899 --> 01:24:32,649 shaped objects in front of a mass spectrometer so you don't have to do 939 01:24:32,649 --> 01:24:37,570 sample preparation in order to get some sort of representative spectra of the 940 01:24:37,570 --> 01:24:42,909 surfaces of the samples that you're looking at as you can imagine that 941 01:24:42,909 --> 01:24:47,380 creates a whole host of other questions as what kinds of surfaces how close what 942 01:24:47,380 --> 01:24:51,280 compounds how hot those are all parameters that have to be dictated 943 01:24:51,280 --> 01:24:55,899 according to each application but this is the basic approach that dart takes to 944 01:24:55,899 --> 01:25:02,199 producing gas phase ions for mass spectrometry and what does Dart actually 945 01:25:02,199 --> 01:25:06,820 look like in practice we've generated a little movie here one of the advantages 946 01:25:06,820 --> 01:25:12,929 of dart is how fast it is and this will show you a mass spectrum of a little 947 01:25:12,929 --> 01:25:17,169 sample that was introduced you probably maybe saw in an upper right hand corner 948 01:25:17,169 --> 01:25:22,090 a little gap glass capillary came down and was stuck into the dart stream and 949 01:25:22,090 --> 01:25:26,440 you see a peak there at M over Z one seven this was our demonstration of how 950 01:25:26,440 --> 01:25:32,260 melamine is detected in milk products so we coated a little glass capillary with 951 01:25:32,260 --> 01:25:36,400 a milk product and if there was melamine present it was Heian eyes dan M over Z 952 01:25:36,400 --> 01:25:42,639 127 mass of melamine plus h or plus proton jumps up on the screen there and 953 01:25:42,639 --> 01:25:47,440 you can see the time frame there is on the order of 30 seconds or less per 954 01:25:47,440 --> 01:25:54,090 sample so you get an immediate spike in signal and it drops off rather quickly 955 01:25:54,090 --> 01:25:59,230 as fast as your robot can go and pick up another sample or you can go grab 956 01:25:59,230 --> 01:26:03,239 another sample it returns to baseline and you're ready for the next analysis 957 01:26:03,239 --> 01:26:09,280 so what does dart m/s measure well it measures mass spectrum because it's dart 958 01:26:09,280 --> 01:26:13,900 is just an ionization TKE technique for a mass spectrometer in this case we 959 01:26:13,900 --> 01:26:20,500 interface dart with a Watters última which is just a simple triple quad and 960 01:26:20,500 --> 01:26:25,510 we looked at the mass spectrum because of the way that we set up the dart and 961 01:26:25,510 --> 01:26:29,860 because of the mass spec you can see a couple of diagnostic ions here for in 962 01:26:29,860 --> 01:26:35,349 this case diethyl hexyl phthalates you see the molecular ion the n plus h some 963 01:26:35,349 --> 01:26:38,199 of the characteristic fragment ions we were running this under some slightly 964 01:26:38,199 --> 01:26:43,360 fragmenting conditions and if you use different mass spectrometers you get 965 01:26:43,360 --> 01:26:46,929 different results so the bottom trace here is the mass spectrum of the same 966 01:26:46,929 --> 01:26:52,179 standard using a Joel acute off which is just a low-end time-of-flight mass 967 01:26:52,179 --> 01:26:58,510 spectrometer about 170 K for one of those and as you can see there even in 968 01:26:58,510 --> 01:27:03,429 the presence of a mix standard this happened to have a little di n pol di DP 969 01:27:03,429 --> 01:27:09,460 and some teh P you can see the dominant ion because of the chyme on the trace 970 01:27:09,460 --> 01:27:16,570 that I picked was that well the octal phthalate I should say signal and the 971 01:27:16,570 --> 01:27:21,400 nice thing about using a toss is of course the added mass accuracy as you 972 01:27:21,400 --> 01:27:27,130 can see you get high mass accuracy M to a certain degree a good mass resolution 973 01:27:27,130 --> 01:27:30,070 there's certainly other mass spectrometers that can achieve better 974 01:27:30,070 --> 01:27:35,700 but the point being that when you're doing direct analysis or atmospheric is 975 01:27:35,700 --> 01:27:40,560 analysis you're gonna get mixtures and you no longer are using chromatography 976 01:27:40,560 --> 01:27:45,150 to help separate your chemicals previous to analysis so anything that you can do 977 01:27:45,150 --> 01:27:49,380 to help you differentiate one molecule from another can help and accurate and 978 01:27:49,380 --> 01:27:54,390 high res mass spec can help with that so what does the dart ms response look 979 01:27:54,390 --> 01:27:57,060 like well you're not using chromatography so you don't have a 980 01:27:57,060 --> 01:28:02,370 chromatogram now you just have a time trace this is a typical total ion 981 01:28:02,370 --> 01:28:05,760 current it's not a total item chromatogram there's no chromatography 982 01:28:05,760 --> 01:28:13,080 of a couple of sample introductions in front of a dart and in this case this is 983 01:28:13,080 --> 01:28:18,630 from a triple quad the waters that I was mentioning and you see the TIC rise and 984 01:28:18,630 --> 01:28:23,820 fall but rather noisily and rather air reproducibly but when you go to look at 985 01:28:23,820 --> 01:28:28,820 a particular compound of interest you see that the trace is a lot more easy to 986 01:28:28,820 --> 01:28:35,640 understand and in this case the the dhp standard of various concentrations gave 987 01:28:35,640 --> 01:28:40,200 a very predictable response as a function of time so again we're looking 988 01:28:40,200 --> 01:28:45,090 at a mass spectrum as a function of time so what are all the different dark 989 01:28:45,090 --> 01:28:50,010 configurations that I've been discussing well we started off in our laboratory 990 01:28:50,010 --> 01:28:54,180 with a first generation dart which is kind of a clunky looking thing and in 991 01:28:54,180 --> 01:28:58,560 this particular case we are using a robotic auto sampler to place little 992 01:28:58,560 --> 01:29:02,640 strips of particular polymers into the dart stream you'll see a little glass 993 01:29:02,640 --> 01:29:07,890 capillary tube sticking out that helps transfer the gas stream from the 994 01:29:07,890 --> 01:29:10,890 ionization region into the mass spectrometer and because the 995 01:29:10,890 --> 01:29:16,500 manufacturer of the dart ion source had not interfaced this particular mass 996 01:29:16,500 --> 01:29:20,190 spectrometer we literally just terminated the glass tube immediately 997 01:29:20,190 --> 01:29:25,230 adjacent to the mass spectrometer Inlet it wasn't even on axis and so in that 998 01:29:25,230 --> 01:29:29,820 case our sensitivity was quite poor and the results that we generate with this 999 01:29:29,820 --> 01:29:33,120 configuration weren't really translatable to a lot of the people who 1000 01:29:33,120 --> 01:29:38,370 had purchased the Jol acute off switch was the parent company of the ion source 1001 01:29:38,370 --> 01:29:44,360 manufacturer dart is manufactured by iron sights 1002 01:29:44,360 --> 01:29:50,060 out of p body mass we subsequently purchased two other configurations at 1003 01:29:50,060 --> 01:29:55,730 dart Orbitrap in a dart a cute off so this is the joel a cute off and the 1004 01:29:55,730 --> 01:30:00,260 newest version of their dart source that goes with the a cute off again as you 1005 01:30:00,260 --> 01:30:05,750 can see here the the silver cone coming out of the mass spectrometer that's the 1006 01:30:05,750 --> 01:30:10,340 inlet the silver and white cones coming off the dart source the that's where the 1007 01:30:10,340 --> 01:30:15,650 gas exits we happen to be running a little homemade rail linear rail through 1008 01:30:15,650 --> 01:30:19,040 the dart source at this particular case we were mapping some chemical 1009 01:30:19,040 --> 01:30:23,960 concentrations across the surface of a piece of packaging and we just thought 1010 01:30:23,960 --> 01:30:27,500 we'd try a little linear rail in that particular case but as you can see the 1011 01:30:27,500 --> 01:30:30,949 dart source can be moved back and forth various distances from the mass 1012 01:30:30,949 --> 01:30:34,639 spectrometer Inlet they even have configurations that allow you to raise 1013 01:30:34,639 --> 01:30:39,590 and lower it angle it at different angles and so you really can adjust the 1014 01:30:39,590 --> 01:30:43,280 dart source to fit whatever geometries you need for your particular sand 1015 01:30:43,280 --> 01:30:49,219 samples the beautiful thing about dart is you can stick really crazy shaped 1016 01:30:49,219 --> 01:30:53,000 objects in front of it and you can still get reproducible mass spectrum you don't 1017 01:30:53,000 --> 01:30:56,719 have to mill you don't have to homogenize now you lose all that 1018 01:30:56,719 --> 01:31:02,000 information you lose reproducibility and quantitation and the like because you're 1019 01:31:02,000 --> 01:31:07,429 not looking at the same sample as you would with in in a typical regulatory 1020 01:31:07,429 --> 01:31:11,810 analysis but if you're going to screen stuff and if you want to have an idea of 1021 01:31:11,810 --> 01:31:17,690 what we're on a particular object phthalates or any other compound might 1022 01:31:17,690 --> 01:31:24,080 be for the surfaces of those objects then dart will allow you to to do that 1023 01:31:24,080 --> 01:31:28,429 by looking at only one part of the object at a time or if you're really 1024 01:31:28,429 --> 01:31:32,510 want to cover every surface you could systematically run the whole surface 1025 01:31:32,510 --> 01:31:38,420 through there but in either case dart is a quick way for a laboratory worker to 1026 01:31:38,420 --> 01:31:43,280 look at a sample without having to do prep and without cross-contamination 1027 01:31:43,280 --> 01:31:46,190 because there's nothing to contaminate here the entrance to the mass 1028 01:31:46,190 --> 01:31:51,770 spectrometer which is going to be less contaminated than if you inject a plug 1029 01:31:51,770 --> 01:31:58,159 of solvent from from a GC system so it's it's got some advantages that way 1030 01:31:58,159 --> 01:32:03,530 here's another angle us introducing a little piece of of packaging you can do 1031 01:32:03,530 --> 01:32:07,790 it manually you can use linear rails they've got transmission configurations 1032 01:32:07,790 --> 01:32:14,599 where you can deposit extracts onto little gridded wire meshes and the and 1033 01:32:14,599 --> 01:32:18,860 the helium flows through the wire mesh and dissolves whatever was on the 1034 01:32:18,860 --> 01:32:23,270 solution that deposited on the grid you know there's lots of configurations for 1035 01:32:23,270 --> 01:32:28,310 introducing samples via dart so can it quantitate that's the big question and 1036 01:32:28,310 --> 01:32:33,619 the answer is no so these are some just some straight-up 1037 01:32:33,619 --> 01:32:39,590 solvent calibration solutions and just measuring the peak height of the mass 1038 01:32:39,590 --> 01:32:43,070 effect signal for diethyl hexyl file a very simple task 1039 01:32:43,070 --> 01:32:49,420 not at all linear not very reproducible at that and the reason is is that 1040 01:32:49,420 --> 01:32:53,780 various amounts of materials are deposited onto the tip of the glass 1041 01:32:53,780 --> 01:32:58,699 capillary that we use to sample the liquids in GC you're using a syringe to 1042 01:32:58,699 --> 01:33:04,550 deliver exactly one microliter every single time whereas in dart the current 1043 01:33:04,550 --> 01:33:08,780 autosampler configuration dips a melting point capillary into your liquid 1044 01:33:08,780 --> 01:33:14,570 solution and depending on how clean that capillary is how far it's dipped in how 1045 01:33:14,570 --> 01:33:21,139 quickly you know what was there a drop shaken off the capillary in the robots 1046 01:33:21,139 --> 01:33:25,010 movements over to the dart you get various quantities deposited on the 1047 01:33:25,010 --> 01:33:28,790 surface and then how fast you scan it through there were there any air 1048 01:33:28,790 --> 01:33:33,650 disturbances in the lab that shifted gas flow patterns it desorbs a different 1049 01:33:33,650 --> 01:33:37,130 amount of material off of that and a different amount makes it into the mass 1050 01:33:37,130 --> 01:33:41,599 spec and a different ion signal but one way to account for all those differences 1051 01:33:41,599 --> 01:33:46,010 is internal standards you know in GCMs we often do that you get very nice 1052 01:33:46,010 --> 01:33:49,579 linear calibration curves when you internal standard normalize your 1053 01:33:49,579 --> 01:33:55,280 responses can also it also helps you with troubleshooting issues in your 1054 01:33:55,280 --> 01:34:00,139 methodology recovery correction you don't have to take you don't have to do 1055 01:34:00,139 --> 01:34:04,969 quantitative transfers all of those things are helped by internal standards 1056 01:34:04,969 --> 01:34:09,110 and so is dart calibration when you include just two internal standards in 1057 01:34:09,110 --> 01:34:12,949 this case for these suite of Leites that you see on the bottom right 1058 01:34:12,949 --> 01:34:17,900 I included a labeled standard of diethyl phthalate and a label of diethyl hexyl 1059 01:34:17,900 --> 01:34:23,749 phthalates and then normalized to one of those to the relative response is quite 1060 01:34:23,749 --> 01:34:30,709 linear and you know R Squared's that we go on about all better than 0.995 but 1061 01:34:30,709 --> 01:34:35,479 when you look at them on a log scale you see GCMs is still much more linear than 1062 01:34:35,479 --> 01:34:40,880 dark and that makes sense your just a lot more controlled sample 1063 01:34:40,880 --> 01:34:48,650 introduction a lot more controlled ion transfer into the inlet not to say that 1064 01:34:48,650 --> 01:34:52,459 it can't be useful you can't get good semi quantitative specially out of 1065 01:34:52,459 --> 01:34:57,050 liquid solutions but it's never going to be the same as GCMs and i would like to 1066 01:34:57,050 --> 01:35:00,949 point out this is over five orders of magnitude so clearly a very broad range 1067 01:35:00,949 --> 01:35:08,689 here and and but it's still GCMs is the gold standard for quantitation so it can 1068 01:35:08,689 --> 01:35:13,429 quantitate in solutions but we're not looking at solutions we're looking at 1069 01:35:13,429 --> 01:35:18,590 surfaces so how sensitive is dart when it comes to looking at surfaces well we 1070 01:35:18,590 --> 01:35:25,249 had another project where we were looking at photo initiators transferring 1071 01:35:25,249 --> 01:35:29,539 from the print side of a printed piece of food packaging to the food contact 1072 01:35:29,539 --> 01:35:34,610 side of an adjacent piece of food packaging it's called set-off and we 1073 01:35:34,610 --> 01:35:38,869 decided to look at err geekier 180 for a common photo initiator by producing 1074 01:35:38,869 --> 01:35:43,880 standard samples with various levels of the photo initiator on the surface of 1075 01:35:43,880 --> 01:35:50,840 the polymer this I believe was in LDPE film and what we saw was just some of 1076 01:35:50,840 --> 01:35:55,329 the concentrations of the samples that we prepared you can see that the 1077 01:35:55,329 --> 01:36:00,260 surficial concentrations at dart which dart is able to differentiate from the 1078 01:36:00,260 --> 01:36:06,739 blanks is right around 0.25 nanograms per square centimeter so definitely down 1079 01:36:06,739 --> 01:36:14,989 in the low fractions of a hundredths of a percent level you're going to see 1080 01:36:14,989 --> 01:36:18,979 surficial concentrations orders of magnitude higher if you're looking at 1081 01:36:18,979 --> 01:36:25,190 even 0.1% phthalates in a polymer so clearly it's 1082 01:36:25,190 --> 01:36:28,520 more than sensitive enough for these types of compounds we haven't done this 1083 01:36:28,520 --> 01:36:33,650 exact procedure with phthalates but the responsiveness of dart and area 2 of 1084 01:36:33,650 --> 01:36:37,400 dart to area cure and phthalates is very comparable they're both small molecules 1085 01:36:37,400 --> 01:36:40,520 I think this vapor pressure of this compound is almost exactly the same as 1086 01:36:40,520 --> 01:36:44,660 diethyl hexyl phthalates vapor pressure is a pretty big factor when you're 1087 01:36:44,660 --> 01:36:49,130 thermally desorbing something off of a surface so we see pretty comparable 1088 01:36:49,130 --> 01:36:53,690 responses in that case i expensed expect the sensitivity for phthalates to be 1089 01:36:53,690 --> 01:36:58,699 very comparable and then we also need the technique to identify the phthalates 1090 01:36:58,699 --> 01:37:03,199 and in particular the nice thing about dart as I showed you back at the 1091 01:37:03,199 --> 01:37:07,070 beginning is it produces almost exclusively molecular ion that is M plus 1092 01:37:07,070 --> 01:37:10,730 h you know one of the reasons why we like to use chemical ionization it's a 1093 01:37:10,730 --> 01:37:14,810 much softer ionization technique it doesn't give you as reproducible mass 1094 01:37:14,810 --> 01:37:20,930 spectrum on those fragment ions but it gives you a lot of very specific 1095 01:37:20,930 --> 01:37:26,690 molecular ion to work with you can also include a little ammonia hydroxide in in 1096 01:37:26,690 --> 01:37:30,440 the lab environment or swab it onto the surface of a polymer and you can produce 1097 01:37:30,440 --> 01:37:37,489 ammonia instead of protonated molecule ions so instead of m plus h SN + NH 4 1098 01:37:37,489 --> 01:37:41,510 it's often a common technique to look at both of those ions as a way of 1099 01:37:41,510 --> 01:37:48,590 confirming that you know the 195 iron you see is really corresponding to to 1100 01:37:48,590 --> 01:37:54,860 dimethyl phthalates or whatnot and as we all know this m plus h ion is very 1101 01:37:54,860 --> 01:37:59,690 useful the fragment ions help a little bit more but isomers produce all the 1102 01:37:59,690 --> 01:38:03,469 same ions in theory and they should because there i Cerner's they're 1103 01:38:03,469 --> 01:38:07,880 positional isomers so diethyl hexyl phthalates and octal phthalates are 1104 01:38:07,880 --> 01:38:14,719 perfect example and other work by other folks including Roth and Bakker and and 1105 01:38:14,719 --> 01:38:19,489 SH walk it published in rapid communication and mass spec took a close 1106 01:38:19,489 --> 01:38:23,600 look at this I think cooky out of Hungary also did the same thing in 1107 01:38:23,600 --> 01:38:31,340 international mass spec Journal and what they found is the 261 to 279 the the 1108 01:38:31,340 --> 01:38:37,280 Ethne minus ethylene and minus ethanol fragments are produced in differential 1109 01:38:37,280 --> 01:38:40,780 ratios and that really froze up and you can 1110 01:38:40,780 --> 01:38:45,250 differentiate ethyl hexlen and octal that way the trouble is a lot of things 1111 01:38:45,250 --> 01:38:52,600 can produce 261 and 279 and pretty much any isomeric octal phthalates can do 1112 01:38:52,600 --> 01:38:56,949 that to varying degrees and what if you have mixtures of these phthalates so 1113 01:38:56,949 --> 01:39:02,500 when we looked at a particular PP and LDPE film for various phthalates we see 1114 01:39:02,500 --> 01:39:07,449 the molecular ions of ethyl Hextall or an octal and also dye I so know no 1115 01:39:07,449 --> 01:39:12,910 phthalates when we look at the iron ratios of the fragments 279 clearly it 1116 01:39:12,910 --> 01:39:19,750 exceeds 261 suggesting it's ethyl hexo phthalates you know the ratio is 1.7 but 1117 01:39:19,750 --> 01:39:25,270 in the standards that ratio was 3.3 so what does this mean and in our initial 1118 01:39:25,270 --> 01:39:29,170 analysis of this sample which is the cookie bar at the bottom of the chart 1119 01:39:29,170 --> 01:39:34,000 there we said that we thought there's low hundreds of nanograms per square 1120 01:39:34,000 --> 01:39:38,680 centimeter of diethyl hexyl phthalates and we didn't think there was an octal 1121 01:39:38,680 --> 01:39:44,050 phthalates we then subjected these same samples to extraction LCMS analysis 1122 01:39:44,050 --> 01:39:49,000 here's the chromatogram and we focused a lot on that isononyl phthalates in that 1123 01:39:49,000 --> 01:39:55,690 particular case and what we saw was a very odd shape lcms peak we expect nice 1124 01:39:55,690 --> 01:40:00,820 sharp lcms Peaks for the ice and onal and we suspected it was an N octave 1125 01:40:00,820 --> 01:40:06,460 Dessel phthalates which would be a particular structural isomer of of the 1126 01:40:06,460 --> 01:40:10,780 no no phthalates and sure enough when we spiked it with an additional hundred ppb 1127 01:40:10,780 --> 01:40:16,719 of dinnah that small shoulder goes up so din up is the shoulder and n octave 1128 01:40:16,719 --> 01:40:20,320 Dessel phthalates was the dominant compound in this particular package 1129 01:40:20,320 --> 01:40:26,020 similar analysis of ethyl hexyl and an octal in this particular and compound 1130 01:40:26,020 --> 01:40:30,250 the cookie bar showed as you can see on the bottom that there was actually 1131 01:40:30,250 --> 01:40:34,870 nearly equivalent concentrations of an octal phthalates and ethyl hexyl 1132 01:40:34,870 --> 01:40:39,460 phthalates that's why our iron ratios of those fragments switched by dart ms and 1133 01:40:39,460 --> 01:40:45,180 we completely missed the anak the daesil phthalates in this particular sample so 1134 01:40:45,180 --> 01:40:50,140 what can we can conclude from all of this well sample positioning effects 1135 01:40:50,140 --> 01:40:54,550 dart response it's more than sensitive enough for phthalate 1136 01:40:54,550 --> 01:40:59,559 analysis it can be quantitative in certain situations when you use internal 1137 01:40:59,559 --> 01:41:03,309 standards and especially with solvents it can be sending semi-quantitative off 1138 01:41:03,309 --> 01:41:07,510 of polymer surfaces especially if you can deposit an internal standard which I 1139 01:41:07,510 --> 01:41:13,329 know some nist groups have been working on for the explosives methods they've 1140 01:41:13,329 --> 01:41:18,849 been working on printing standards on surfaces and it cannot reliably identify 1141 01:41:18,849 --> 01:41:25,420 different isomers of different phthalates not in mixtures and one last 1142 01:41:25,420 --> 01:41:31,690 note is the time responsive dart so this is a typical tick and this is what that 1143 01:41:31,690 --> 01:41:38,440 stand this is a total iron current of a typical standard for Dart and what you 1144 01:41:38,440 --> 01:41:43,570 see here is first the solvent ethyl hexyl phthalates or ethyl acetate excuse 1145 01:41:43,570 --> 01:41:49,719 me came off the surface of the of the tip and then the diethyl hexyl 1146 01:41:49,719 --> 01:41:54,130 phthalates in the last second and the time scales of these are about 1/6 to 1147 01:41:54,130 --> 01:41:59,199 1/9 of a second so you need to be measuring your your mass spectral traces 1148 01:41:59,199 --> 01:42:05,559 at 6 to 9 Hertz at least so cycles per second in order for dart to really be 1149 01:42:05,559 --> 01:42:10,570 useful in capturing the actual quantity law so these are all things that we need 1150 01:42:10,570 --> 01:42:14,289 to keep in mind but again the main points it cannot reliably identify the 1151 01:42:14,289 --> 01:42:17,920 different isomers it can quant under certain circumstances but it can 1152 01:42:17,920 --> 01:42:24,269 certainly screen for the presence of various phthalates thank you 1153 01:42:32,160 --> 01:42:40,060 well if you can reliably move the sample through the dart stream like we were 1154 01:42:40,060 --> 01:42:45,280 doing with that little linear rail on the surface then you can assign a 1155 01:42:45,280 --> 01:42:50,140 spatial map that will be our next publication where we reproduce the set 1156 01:42:50,140 --> 01:42:54,960 off image of a print on the adjacent piece of packaging you can see the same 1157 01:42:54,960 --> 01:43:09,090 trademark logos and you know images but just recreate it in a chemical map well 1158 01:43:09,090 --> 01:43:16,200 so the width of the of the dart beam is on the order of about a centimeter or 1159 01:43:16,200 --> 01:43:20,500 three-quarters of a centimeter somewhere around there I know that they're working 1160 01:43:20,500 --> 01:43:26,880 on different iterations that have narrower helium being widths but really 1161 01:43:26,880 --> 01:43:30,700 double or triple that and that's probably the double that and that's 1162 01:43:30,700 --> 01:43:33,610 probably the smallest scale of resolution you're going to achieve and 1163 01:43:33,610 --> 01:43:37,530 then of course you can screw it up by moving the sample too fast or you're 1164 01:43:37,530 --> 01:43:54,790 reproducibly yeah why don't we go ahead we'll break for lunch now and we'll 1165 01:43:54,790 --> 01:43:58,290 start back up again at one o'clock