Speciated arsenic in air: Measurement methodology and risk assessment considerations

Figures & data

Table 1. Mean (range) of speciated arsenic concentrations in ambient air (ng/m³), grouped by particle size

Study(Reference)	ParticleSize	EnvironmentalSetting	Numberof Samples	As(III)	As(V)	Total As	DMA	MMA	TMA^g	As(III)/As(V)	(As(III) + As(V))/Total
Speciated arsenic in PM2.5
Šlejkovec et al., 2000	<2 µm	U; D	2	ND (<0.01–<0.02)	1.18 (0.84–1.52)	2.4 (2.1–2.6)	ND (<0.05–<0.10)	ND (<0.01–<0.01)			0.49
Šlejkovec et al., 2000	<2 µm	U; AT	2	ND (<0.05–<0.09)	0.21(0.12–0.3)	0.47 (<0.3–0.64)	ND (<0.26–<0.47)	ND (<0.02–<0.03)			0.45
Rabano et al., 1989	<2.5 µm	U	16	7.4 (<1.2–44)	5.2 (<0.9–18.7)					1.42
Sánchez de la Campa et al., 2008	<2.5 µm	U; I	22	1.4 (0.1–2.7)	6.6 (0.01–56.2)	7.9 (1–56.6)				0.21	1.01
Sánchez de la Campa et al., 2008	<2.5 µm	U; I	24	0.9 (0.01–1.6)	5 (0.01–25.3)	6.4 (0.8–30.2)				0.18	0.92
Farinha et al., 2004	<2.5 µm	U; I^a	47	0.09 (NR)	1.14 (NR)	2.71 (NR)				0.079	0.45
Farinha et al., 2004	<2.5 µm	U; I^b	43	0.037 (NR)	0.42 (NR)	1.9 (NR)				0.088	0.24
Tsopelas et al., 2008	<2.5 µm	I^c	16	<0.2 (NR)	1.7 (NR)	1.9 (NR)	<0.5 (NR)	<0.5 (NR)			0.89
Range of mean arsenic concentration in PM2.5				ND-7.4	ND-6.6	0.047–7.9				0.000–1.42	0.24–1.01
Speciated arsenic in PM10
Sánchez-Rodas et al., 2007	<10 µm	U; I	25	1.2 (0.6–2.2)	6.5 (0.01–25.7)	7.7 (1.6–29.4)				0.18	1.00
Sánchez-Rodas et al., 2007	<10 µm	U; I	25	2.1 (0.4–3.4)	7.8 (0.01–77.2)	9.9 (1.3–79.8)				0.27	1.00
Range of mean arsenic concentration in PM10				1.2–2.1	6.5–7.8	7.7–9.9				0.18–0.27	1.00–1.00
Speciated arsenic in coarse PM
Šlejkovec et al., 2000	2–10 µm	U; D	2	ND (<0.01–<0.02)	0.115 (0.08–0.15)	0.96 (0.61–1.3)	ND (<0.05–<0.1)	ND (<0.01–<0.01)			0.12
Šlejkovec et al., 2000	2–10 µm	U; AT	2	ND (<0.09–<0.11)	0.545 (0.41–0.68)	4.5 (3.7–5.3)	ND (<0.47–<0.58)	ND (<0.03–<0.04)			0.12
Farinha et al., 2004	2.5–10 µm	U; I^a	47	0.032 (NR)	0.55 (NR)	0.69 (NR)				0.058	0.84
Farinha et al., 2004	2.5–10 µm	U; I^b	43	0.025 (NR)	^f(NR)	0.15 (NR)					0.17
Tsopelas et al., 2008	2.5–10 µm	I^c	16	<0.2 (NR)	1.0 (NR)	1.1 (NR)	<0.5 (NR)	<0.5 (NR)			0.91
Rabano et al., 1989	>2.5 µm	U	16	1.8 (<0.9–4.8)	2.2 (<0.8–6.6)					0.82
Range of mean arsenic concentration in coarse PM				ND-1.8	0.1–2.2	0.15–4.5				0.00–0.82	0.12–1.00
Speciated arsenic in TSP
Rabano et al., 1989	TSP	U	16			18.9 (2.8–69.4)
Oliveira et al., 2005	TSP	U; I	12	1.2 (0.3–1.8)	10.4 (2.1–30.6)	12.3 (3.0–33.8)	ND (NR)	ND (NR)		0.12	0.94
Solomon et al., 1993	TSP	R; I^d	17	0.54 (0.06–3.08)	2.29 (0.51–6.54)					0.24
Solomon et al., 1993	TSP	Rl; I	19	0.22 (<0.18–<0.3; max detect 0.19)	0.46 (0.08–1.3)					0.48
Mukai and Ambe, 1987b	TSP	R	1				0.017	ND	0.057
Mukai and Ambe, 1987b	TSP	R	1				0.008	ND	0.006
Mukai and Ambe, 1987b	TSP	R	1				0.003	ND	0.02
Mukai and Ambe, 1987b	TSP	R	5				0.025 (0.006–0.053)	0.097 (ND-0.485)	0.177 (0.025–0.604)
Mukai and Ambe, 1987a	TSP	R; AF^e	1				NR (NR-0.43)	NR (NR-1.4)
Tsopelas et al., 2008	TSP	I^c	16	<0.2 (NR)	3.2	3.4	<0.5 (NR)	0.5 (NR)			0.94
Range of mean arsenic concentration in TSP				0.22–1.2	0.46–10.4	12.3–18.9				0.12–0.48	0.94–0.94
Notes: AF = agricultural fields; AT = automobile tunnel; D = downtown; I = industrial; ND = below detection limit; results below ND were replaced with DL in order to calculate averages; NR = not reported; R = rural; U = urban. ^aLocated near a 100-MW coal/oil power plant. ^bLocated near a 1256-MW coal power plant. ^cLocated near refineries and a major highway. ^dLocated in a geothermal development area. ^eLocated 20–30 km away from an area where alkyl-arsenic pesticides were applied in June and early July. ^f Farinha et al. (2004), reported 0.005 ng/m3 of As(V) in the coarse fraction from Sines. This result was based on a single measurement, and it is inconsistent with all other As(V) results in this study (i.e., As(V) concentrations are expected to be higher than As(III) concentrations). Therefore, we have not reported the As(III):As(V) ratio for this result. ^gTrimethyl arsenic.

Table 2. Examples of sample collection and analysis procedures for arsenic in ambient air

Analysis Method	Method Title	Compounds	Sampling Medium	Analysis
NIOSH Method 7900	Arsenic and compounds as As	All arsenic compounds (as As) exceptAsH3 and As2O3	0.8-μm cellulose ester membrane filter	Flame AA, arsine generation
NIOSH Method 5022	Arsenic, organo	MMA, DMA, arsenic acid	PTFE filter	Ion chromatography/hydride AA
NIOSH Method 6001	Arsine	AsH3	Sorbent tube	GFAA
U.S. EPA	Determination of Arsenic in Suspended PM Collected from Ambient Air	Total As	Glass or quartz fiber filters	GFAA
U.S. EPA	Compendium of Methods for  the Determination of  Inorganic Compounds in  Ambient Air	Total As	Multiple analytical methods	GFAA, ICP, ICP/MS, NAA, etc.
References: NIOSH, 1994a; NIOSH, 1994b; NIOSH, 1994c; EPA, 1988; EPA, 1999.

Table 3. Ambient air studies and comparison of study methodologies

Study (Reference)	Particle Size	Arsenic (As) Compounds Analyzed	Collection Method	Extraction Method	Analytical Method	QC Reported	Detection Limit
Johnson and Braman, 1975	<3 µm, >3 µm	Inorganic As; methylarsine, dimethylarsine, trimethylarsine	Low vol/glass fiber filter for particles >0.3 µm14 mm pyrex tube/mesh silver plated pyrex beads	Not specified; alkaline wash/extraction	d.c. discharge—emission spectroscopy	Precision: RSD ± 10%	0.1–0.2 ng/m^3
Mukai and Ambe, 1987b	TSP	MMA, DMA, TMA	Hi-vol; quartz fiber filter	1 M HCl/EDTA/6 mL NaBH4	HG-GC-AAS	Accuracy: %R varied from 86–109%	<3–10 ng/m^3 (for all 3 As species)
Mukai and Ambe, 1987a	TSP	MMA, DMA	Hi-vol; quartz fiber filter	NaOH/HCl/NaBH4	HG-GC-AAS	Accuracy: %R = 92%	∼0.1 ng/m^3
Rabano et al., 1989	<2.5 µm, >2.5 µm, TSP	Total As, As(III), As(V)	TSP: Hi-vol/glass microfiber<PM2.5 and >PM2.5: Hi-vol DCVI/PTFE	Total As: HNO3 As(III)/As(V): Ethanol/HCl	Total As method not specified Speciated As: HG-AAS	Accuracy: corr. (r) = 0.94 for Total As versus As(III) + As(V) Accuracy: %R of standards = 95 ± 7/100 ± 8 for As(III)/As(V) in unexposed filters; 79 ± 22/97 ± 23 for As(III)/As(V) in exposed filters Precision: 8% for unexposed filters, 23% for exposed filters	1 ng/m^3
Solomon et al., 1993; Solomon, 1984	TSP	As(III), As(V)	TSP: Hi-vol/quartz fiber filter	Assumed Zn/HCl/NaBH4	Assumed flame-AAS	Precision: CV = 12–13%	0.25 ng/m^3
Talebi, 1999	TSP	Total As, As(III)	Hi-vol/quartz fiber filter	H2SO4/HNO3/water	Flame-AAS	Not reported	Not reported
Šlejkovec et al., 2000	<2 µm, 2–10 µm	Total As, As(III), As(V), MMA, DMA in coarse (2–10 µm) and fine (<2 µm) particles	Stacked filter units	Methanol/water/KH2PO4	Total As-INAAAs(III), As(V), MMA, DMA: HPLC-HG-AFS	RSD <10%	<0.01 ng/m^3 (As(III), MMA)<0.05 ng/m^3 (DMA); <0.08 ng/m^3 (As(V))
Farinha et al., 2004	<2.5 µm, 2.5–10 µm	As(III)/As(V) in PM2.5–10 and <PM2.5	Not specified; described in Reis et al., 1999	Water/CaCl2/H3PO4	Speciated As: HPLC-UV-HG-AFSTotal As: INAA	Total As: 5% analytical error based on single replicate Accuracy: Extraction efficiency = 20.2–78%	Assumed < 0.05–1.1 ng/m^3
Oliveira et al., 2005	TSP	Total As, As(III), As(V), DMA, MMA	Hi-vol/quartz fiber filters	Compared extraction solutions (water, NH2OH·HCl, and H3PO4) and extraction methods (microwave digestion or ultrasonic radiation)	Speciated As: HPLC-HG-AFS Total As: HG-AFS	Optimal mean recoveries [= (As(III) + As(V))/As Total] for the 12 samples were 86% (for the extraction using H3PO4 + microwave digestion) and 94% (for the extraction using NH2OH·HCl + microwave digestion)Stability study indicated no significant change Accuracy: Extraction efficiency Total As versus As(III) + As(V) = 97–126%	Assume <0.2 ng/m^3
Sánchez-Rodas et al., 2007	<10 µm	As(III), As(V) in PM10	Hi-vol/quartz fiber filter	Speciated as: NH2OH·HCl solution/microwave digestionTotal As: HClO4 + HNO3 + HF + digestion	Speciated As: HPLC-HG-AFS Total As: HG-AFS	Accuracy: Extraction efficiency Total As versus As(III)+As(V) = 91-105%Precision and Accuracy: reported to be in range of 3-10% (includes NIST fly ash SRM for Total As) Stability study indicated no significant change (transformation) among As species	0.1 and 0.4 ng/m^3 for As(III) and As(V), respectively
Sánchez de la Campa et al., 2008	<2.5 µm	As(III) and As(V) in PM2.5	Hi-vol/quartz fiber filters	Speciated As: NH2OH·HCl solution/microwave digestionTotal As: HClO4 + HNO3 + HF + digestion	Speciated As: HPLC-HG-AFS Total As: HG-AFS	Accuracy: Total As SRM %R ∼100 Accuracy: Extraction efficiency Total As versus As(III) and As(V) = 91–104% (mean 97%)	0.1 and 0.4 ng/m^3 for As(III) and As(V), respectively
Tsopelas et al., 2008	<2.5 µm, 2.5–10 µm	As(III), As(V), MMA, DMA in PM10 and PM2.5	Hi-vol TSP/glass fiberHi- and low-vol/stacked PFTE Filters: PM10 and PM2.5	HCl	Total/Speciated As: HG-ICP-OES Ion exchange (separation of As(V), MMA, and DMA)	Accuracy: In method development, %R of standards ranged from 94–106%	As(III): 0.1 ng/m^3 As(V): 0.7 ng/m^3 MMA: 0.3 ng/m^3 DMA: 0.4 ng/m^3
Notes: In cases where detection limits are reported with a < symbol, a DL was not reported, but assumed to be < the lowest detected concentration reported in the article. Sample preparation/extraction is final method selected for study/reported results.

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