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How Much Arsenic Do We Eat? Analytical chemists make light work in tracking potentially harmful chemicals Julian Tyson Department of Chemistry UMass Amherst.

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Presentation on theme: "How Much Arsenic Do We Eat? Analytical chemists make light work in tracking potentially harmful chemicals Julian Tyson Department of Chemistry UMass Amherst."— Presentation transcript:

1 How Much Arsenic Do We Eat? Analytical chemists make light work in tracking potentially harmful chemicals Julian Tyson Department of Chemistry UMass Amherst

2 Analytical chemists provide information about the chemical composition of materials. So that a decision can be taken. Interaction of light with materials. How do analytical chemists make light work in tracking potentially harmful chemicals?

3 Light is a wave and is a form of energy. The energy of light is inversely related to its wavelength. Short wavelength: high energy. Long wavelength: low energy

4 Summary of where we are now. Color of objects is due to the absorption of light. Absorption is due to the molecules. The wavelengths of the light absorbed tell us something about which chemicals are present. Amount of light absorbed depends on the number of molecules in the light beam, so The extent of the absorption tells us something about how much of a chemical is present.

5 Analytical chemists use the interaction of light with with molecules that contain arsenic to measure the arsenic in relevant materials.

6 So how does arsenic get into relevant materials? Arsenic occurs in nature. It is about the 40 th most abundant element on the planet. Geological processes have spread it around. Weve extracted it from ores, made useful compounds and spread them around. Open ocean water: about 1 - 4 ppb River and surface water: about 0.1 - 1 ppb

7 Realgar As 4 S 4 Arsenic trioxide As 2 O 3 Arsenic As Orpiment As 2 S 3 The arsenic in the environment story

8 Ground water: a major problem around the world. Especially in SE Asia (Bangladesh and West Bengal, India) Concentrations: 0.1 – 1000 ppb. US EPA limit is 10 ppb

9 Concentrations in soil are about 2 mg kg -1. But there are considerable variations and theres a legacy of previous agricultural practice to deal with.

10 Amounts. Weight: 1 kilogram (kg) = 2.2 lb = 1,000 grams (g) 1 milligram (mg) = one-thousandth of a gram 1 microgram (µg) = one-millionth of a gram. A grain of salt weighs 2 mg (the official grain is 65 mg) Amounts. Volume: liter (L) = 0.26 gallon (US) = 1,000 milliliters (mL) 1 milliliter (mL) = one-thousandth of a liter 1 microliter (µL) = one-millionth of a liter A drop (of water) is about 50 µL A bathtub contains about 230 L

11 Concentrations in solids: mass per mass 1 part per million (ppm) is 1 milligram in 1 kilogram i.e. 1 mg/kg or 1 microgram in 1 gram i.e. 1 µg/g Scientist sometimes write this as 1 µg g -1 A part per billion (ppb) is 1 µg kg -1 Concentrations in liquids: mass per volume 1 part per million (ppm) is 1 milligram in 1 liter i.e. 1 mg/L or 1 microgram in 1 mL i.e. 1 µg/mL Scientist sometimes write this as 1 µg mL -1 A part per billion (ppb) is 1 µg L -1 1000 ppb = 1 ppm

12 One grain weighs 65 mg (2.5 mm cube of As 2 O 3 ) 76% by weight is As 49 mg 21 bathtubs contain 21 x 233 L = 4,900 L 1 grain in 21 bathtubs = 10 ppb The US EPA limit for arsenic in drinking water How to make a 10 pbb solution

13 Arsenic speciation There are a lot of different arsenic compounds in the environment. Inorganic Arsenic bonded to oxygen and/or sulfur or hydrogen. As 2 O 5 H 3 AsO 4 arsenate As 2 O 3 H 3 AsO 3 arsenite AsH 3 arsine Organic Arsenic bonded to carbon and/or oxygen or hydrogen Methylated arsenate CH 3 AsO(OH) 2 MMA (CH 3 ) 2 As(O)OH DMA Arsenobetaine, arsenocholine

14 Some formulae for the chemists in the audience. arsenite dimethylarsinate arsenatemonomethylarsonate cacodylate trimethylarsine oxide

15 More formulae for the chemists in the audience. trimethylarsine oxidetetramethylarsonium

16 Yet more formulae for the chemists in the audience. arsenocholine Seafood arsenic TETRA arsenobetaine

17 Not all arsenic compounds are very toxic Some arsenic compounds are non-toxic. arsenobetaine and arsenocholine and arsenosugars seafood arsenic OK - all chemicals are toxic: it all depends on the dose and how you interact with them. Some arsenic compounds are toxic Acute lethal dose of As 2 O 3 is about 100 mg for a 70-kg adult. About 2 grains or a 3 mm cube. Some arsenic compounds are sort of non-toxic Monomethyl and dimethyl arsenates The adverse health effect of concern is cancer.

18 How does arsenic get into our food? Plants take up arsenic compounds from the soil. Legacy of previous applications.

19 How arsenic gets into crops

20 How do we know whether food and drink contains potentially harmful forms of arsenic? Ask the analytical chemists. They tell us. Seafood contains non-toxic forms Drinking water contains toxic, inorganic forms Food contains toxic (inorganic) and sort-of toxic forms (mono- and di- methylated). Approach : Measure total arsenic and assume it is all toxic. If less than guideline value: no problem If more than guideline value: more analysis needed

21 How much arsenic is considered safe? How much inorganic arsenic is considered safe? Food: No US guideline value. Drinking water: US EPA 10 µg L -1 (ppb) Joint FAO/WHO expert committee on food additives, seventy-second meeting, Rome, 16–25 February 2010, summary and conclusions Issued 16th March 2010 http://www.who.int/foodsafety/chem/summary72_rev.pdf The limit for dietary inorganic arsenic exposure is: 3.0 µg per kg body weight per day

22 How much inorganic arsenic is considered safe? Dietary: 3.0 µg per kg body weight per day. Developmental stage Weight lbs 1 lb = 0.45 kg Tolerable daily intake µg Newborn79 1-year-old2230 5-year-old4257 teenager140 (m) 117 (f)191 (m) 160 (f) young adult155 (m) 127 (f)211 (m) 173 (f) Adult (US average)191 (m) 164 (f)260 (m) 224 (f) football player300409 overweightyour call> 400 Acute lethal dose (adult) 100 mg

23 How much inorganic arsenic do we actually eat? Food: Ask the analytical chemists. Developmental stage Weight lbs 1 lb = 0.45 kg Tolerable daily intake µg Newborn79 1-year-old2230 5-year-old4257 teenager140 (m) 117 (f)191 (m) 160 (f) young adult155 (m) 127 (f)211 (m) 173 (f) Adult (US average)191 (m) 164 (f)260 (m) 224 (f) football player300409 overweightyour call> 400 Acute lethal dose (adult) 100 mg

24 Food and Chemical Toxicology 37 (1999) 839-846 Examined 40 commodities expected to deliver 90% of total dietary inorganic arsenic. Took 4 samples of each. Measured total arsenic and inorganic arsenic. A market basket survey of inorganic food in rice

25 FoodTotal arsenic µg kg -1 wet weight Inorganic arsenic µg kg -1 wet weight saltwater finfish2,4000.5 shrimp1,9002 tuna5121 rice30374 chicken861 grape juice589 beef520.4 peanut butter445 watermelon409 flour3911 spinach56 apple juice83

26 Inorganic arsenic. Environmental Health Perspectives, 2010, 118, 345-350 Probabilistic modeling of dietary arsenic exposure and dose and evaluation with 2003-2004 NHANES Data Scientists at US EPA, National Taiwan University, and the Environmental and Occupational Health Sciences Institute 24 12 17 18 13 11 5

27 Environmental Health Perspectives, 2010, 118, 345-350 Results: Mean total exposure from food is 0.38 µg per kg body weight per day. 14-times higher than the mean exposure from drinking water. Exposure from food is 0.05 µg per kg body weight per day i.e. 1.96 µg per day. Approximately 10% of exposure from food is the toxic inorganic form of arsenic. The average American weighs 40 kg i.e. 88 lbs.

28 AgeNumberAverage5 th percentile 99 th percentile 0 - 17570.620.052.08 1 - 21,0680.540.055.06 3 -59630.540.035.6 6-122,1900.370.024.28 13 -193,5760.250.013.58 20 - 494,2210.330.014.12 >503,8040.320.014.91 All16,9310.360.014.45 Calculated exposure from food. Total arsenic: µg per kg body weight per day

29 AgeNumberAverage5 th percentile 99 th percentile 0 - 17570.230.010.8 1 - 21,0680.10.010.59 3 -59630.0800.4 6-122,1900.0400.25 13 -193,5760.0300.21 20 - 494,2210.0300.28 >503,8040.0300.22 All16, 9310.0500.41 Calculated exposure from food. Inorganic arsenic: µg per kg body weight per day

30 FoodTotal arsenic µg kg -1 wet weight Inorganic arsenic µg kg -1 wet weight rice30374 Total arsenic InorganicMMADMAI + MMA + DMA % missing 33555ND 5584 21862ND6112344 46281320228638 196972991980 Theres a problem with the Schoof analysis of the rice. The Schoof report: A market basket survey of inorganic food in rice

31 What do other researchers find about arsenic in rice? Survey of total arsenic and arsenic speciation in US-produced rice as a reference point for evaluating change and future trends. Heitkemper and colleagues at USFDA Cincinnati The average total content was 210 µg kg -1. Regardless of total content, inorganic arsenic rarely exceeded 150 µg kg -1. Arsenic content in US rice has been relatively constant over the past 30 years. Food Additives and Contaminants: Part B, 2009, 2, 112-120

32 DateLocationTotalInorganic% missing* 1980-81LA167105-9 1980-81AR18479-11 1980-81TX445 # 1110 1980-81CA6261-33 1980-81AVE US20290-13 2001-02AVE US26498-11 # One sample had over 1000 µg kg -1 total: inorganic 150 µg kg -1 All values in µg kg -1 based on dry weight. *The minus sign means that the sum of I + MMA + DMA > total

33 In comparison with inorganic arsenic, much less is known regarding the toxicity and biotransformation pathways associated with dietary intake of DMA. Although generally considered to be less toxic than inorganic arsenic, more information about the long- term exposure effects of DMA may be necessary to evaluate fully the risk of rice consumption, given the high DMA content that has been reported in rice. Heitkemper and colleagues at US FDA Cincinnati Conclusions

34 What do other researchers find about arsenic in rice? Meharg and colleagues at the University of Aberdeen

35 Arsenic in rice around the world. All values in µg kg -1 LocationAverage Total Max totalAverage inorganic Max inorganic Bangladesh13033080210 China140460160380 Egypt50580No data France280560No data India701803070 Italy150330110160 Japan190420No data Spain200820No data Thailand140390No data USA250660100150

36 The modeling outlined here indicates that eating rice at typical SE Asia consumption rates, or at higher percentile consumption rates in developed countries, constitutes a significant excess cancer risk to those populations, well above the targets set by US EPA and WHO for carcinogenic sources. As cancers caused by chronic exposure to arsenic sources have a latency of approx. 20 years, the data presented here suggest that long-term epidemiological studies need to be undertaken to characterize this risk. Meharg and colleagues at the University of Aberdeen Conclusions

37 Researchers call for monitoring of arsenic levels in rice By Elizabeth Weise, USA TODAY Dec 5, 2011 Proceedings of the National Academy of Sciences of the USA Dec 5 th 2011 Rice consumption contributes to arsenic exposure in US women Diane Gilbert-Diamond and coworkers at Dartmouth College Emerging data indicate that rice consumption may lead to potentially harmful arsenic exposure. Although inorganic arsenic is thought to be more harmful that DMA, further epidemiological studies are needed to better understand the health risks of DMA... It is imperative that the health impact of arsenic exposure through rice consumption be characterized. www.pnas.org/cgi/doi/10/.1073/pnas1109127108

38 How Much Arsenic Do We Eat? The question really should be: How much inorganic arsenic and methylated arsenic do we eat? Answer: depends on what foods we eat. Rice has a much higher concentration than any other food. What sort of rice, where from and how much. White rice contains less arsenic than brown rice. Where grown. USA, France, and Spain (max total) China, Bangladesh and Italy (max inorganic). Bioavailable? Assume 100%.

39 So. What about apple juice?

40 88 samples purchased in Aug and Sept 2011 in CT, NJ, and NY.

41 Theres no federal limit for arsenic in juice. 25% of samples exceeded 5 ppb and 10% exceeded 10 ppb. Recommended dietary limit is 3 µg per kg body weight per day. 30 - 60 µg for young children. Need to drink 1.2 – 2.4 L i.e. 2.5 – 5 pints per day.

42 Take digital picture with digital camera.


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