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An Agency of the Health and Safety Executive www.hsl.gov.uk An Agency of the Health and Safety Executive
Arsenic speciation in urine using µLC ICP-MS for routine biological monitoring – A two year study
Elizabeth Leese, Jackie Morton and Vikki Carolan
Email – [email protected]
ISBM – Wednesday 11th September 2013
An Agency of the Health and Safety Executive
Introduction
• Arsenic & exposure
• Workplace exposure
• µLC-ICP-MS separation technique
• Background Levels study
• 2 year semi-conductor workplace study
An Agency of the Health and Safety Executive
Arsenic
• Found in all rock, soil, water and air.
• Ranked – 20th most abundant element in the earths crust
– 14th in seawater
– 12th human body
• Classified as a group 1 carcinogen by IARC – Cancer of the skin, lung, kidney and bladder.
– Vomiting, abdominal pain, weakness, diarrhoea and muscle cramps.
• Exposure – Inhalation
– Ingestion
– Dermal
An Agency of the Health and Safety Executive
Species of Arsenic
Monomethylarsonite (MMA3+)
Dimethylarsinite (DMA3+)
Arsenite As3+
Arsenate As5+
Dimethylarsinate (DMA5+)
Monomethylarsonate (MMA5+)
Arsenocholine, AC
Trimethylarsonioacetate Arsenobetaine, AB
An Agency of the Health and Safety Executive
Arsenic Exposure
• Environmental & Dietary
– Cigarettes
– Shellfish & Seafood
– Poultry
– Grain e.g. rice
– Red wine / real ale
– Soil and water
An Agency of the Health and Safety Executive
Arsenic Exposure Worldwide
http://www.bgs.ac.uk/arsenic/
An Agency of the Health and Safety Executive
Arsenic Exposure
• Occupational – Semi Conductor Industry
– Glass Production / Recycling
– Wood Preservation / burning preserved wood
– Pesticide manufacture / application
– Power plants burning arsenic rich coal
– Mining, smelting & landfill
An Agency of the Health and Safety Executive
Urinary Arsenic Analysis – Problem 1
• Total Arsenic
– A total element value is not helpful when assessing exposure, because its unable to distinguish dietary arsenic from toxic inorganic arsenic
• Hydride / Extraction techniques
– Difficulty reducing methylated metabolites • Under estimation
– Food & drink containing methylated metabolites
e.g. rice, red wine & seafood • Over estimation
An Agency of the Health and Safety Executive
Arsenic Speciation - µLC-ICP-MS
• Allows separation of individual species
• Species of Interest
– Inorganic - As3+ As5+
– Methylated Metabolites – DMA5+ MMA5+
– Dietary – AB.
An Agency of the Health and Safety Executive
Separation Technique
ICP-MS
Thermo Scientific XSERIES 2
ESI OneFAST
• 6 port switching value
• 1 ml sample loop
• 50x4mm ID Dionex AG7 column
Mobile Phase A – 2 mM Ammonium carbonate
Mobile Phase B – 70 mM Ammonium carbonate
As3+
As5+ MMA
DMA
AB
1 µg/L Standard
As3+
As5+ MMA
DMA
AB
10 µg/L spiked urine
An Agency of the Health and Safety Executive
Urinary Arsenic Analysis – Problem 2
• Lack of unexposed Background Reference Values
• NO UK Guidance Values
• Drinking water
– EU 10 µg/L total arsenic
– US & WHO 10 µg/L inorganic arsenic
• Biological Samples
– US BEI 35 µg/L summation of inorganic &
– German BAT 50 µg/L metabolites NO AB
• Population studies from unexposed individuals
Most studies people are asked to abstain from eating shellfish and seafood.
An Agency of the Health and Safety Executive
Background Levels Study
• 95 urine samples collected from 53 males and 42 females (>18 years old)
• Not occupationally exposed to arsenic
• Questionnaire returned with urine sample
– Gender / Date of birth
– Smoking habits
– Dietary supplement
– Diet of previous 7 days • Fish Shellfish Seaweed
• Rice Mushrooms Poultry
• Red wine Real ale Bran / germ
An Agency of the Health and Safety Executive
Background Levels Results
Health Canada – Human Biomonitoring of Environmental Chemicals in Canada. n= 6400
US NHANES – National Report on Human Exposure to Environmental Chemicals. n=2557
As3+ As5+ MMA DMA AB
HSL n=95
µg/L µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
95th percentile 0.54 0.99 0.23 0.35 2.37 3.08 12.68 16.08 126.7 174.7
Mean 0.18 0.30 0.06 0.09 0.78 1.33 4.10 7.09 28.69 51.30
As3+ As5+ MMA DMA AB
µg/L µg/L µg/L µg/L µg/L
Health Canada 95th percentile
4.5 <LOD 3.0 30 110
US NHANES 95th percentile
<LOD 1.10 2.40 16.0 35.0
An Agency of the Health and Safety Executive
Background Levels Results µmol/mol creatinine As3+ As5+ MMA DMA AB
Seafood n=66
Mean 0.31 0.09 1.61 8.76 72.06
Range <LOD – 2.3 <LOD – 0.63 <LOD – 13.9 0.9 - 104 0.3 - 1090
NO seafood n=29
Mean 0.29 0.08 0.70 3.31 4.06
Range <LOD – 1.1 <LOD – 0.56 0.2 – 1.9 0.6 – 7.5 0.1 – 47.8
Red wine (NO seafood) n=9
Mean 0.29 0.16 0.81 4.0 4.6
Range 0.07 – 0.54 <LOD – 0.56 0.3 – 1.3 1.9 – 7.5 0.7 – 47.8
NO wine or seafood n =20
Mean 0.29 0.05 0.65 3.02 2.44
Range 0.03 – 1.1 <LOD – 0.31 0.2 – 1.9 0.6 – 5.2 0.1 – 9.8
An Agency of the Health and Safety Executive
2 Year Occupational Study
• Semi-conductors
• Pre & Post samples
– Spring
– Autumn
• 91 workers (54 males & 25 females)
• 441 urine samples
– 203 paired pre and post samples
– 35 single samples
An Agency of the Health and Safety Executive
2 Year Occupational Study Results
Semi-conductors
As3+ As5+ MMA DMA AB
n=441 µg/L µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
Mean 0.10 0.12 0.11 0.13 0.58 0.72 3.5 4.2 29.6 37.9
95th percentile 0.31 0.39 0.28 0.45 1.48 1.87 11.4 14.1 111.3 162.8
Unexposed Background
As3+ As5+ MMA DMA AB
n=95 µg/L µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
µg/L
µmol/mol creatinine
Mean 0.18 0.30 0.06 0.09 0.78 1.33 4.10 7.09 28.69 51.30
95th percentile 0.54 0.99 0.23 0.35 2.37 3.08 12.68 16.08 126.7 174.7
An Agency of the Health and Safety Executive
Summary
An arsenic speciation method has been used to establish urinary background levels for five arsenic species in a UK population
A two year semi-conductor occupational study showed workers were not exposed.
• Reproducible
• Low LOQs
• Good external quality assurance (GEQAS)
An Agency of the Health and Safety Executive
Thank you