Emissions of Particulate Trace Elements, Metals and Organic Species from Gasoline, Diesel, and Biodiesel Passenger Vehicles and Their Relation to Oxidative Potential

Figures & data

TABLE 1 (a) Fuel properties of the petrodiesel used in the Golf vehicle

Properties	Units	Petroleum diesel	EN 590 limits	Test method
Viscosity (40°C)	mm^2 s^−1	3.61	2.00–4.50	EN ISO 3104
Density (15°C)	g cm^–3	0.8345	0.820–0.845	EN ISO 3675
Flash point	°C	71	55 min	EN 22719
Sulfur content	μ g g^–1	29	50 max	EN ISO 20846
Water content	μ g g^–1	52	200 max	EN ISO 12937
Cold filter plugging point (CFPP)	°C	–9	+ 5 max	EN 116
Cetane number		55.5	51 min	EN ISO 5165
Distillation				EN ISO 3405
Initial boiling point (IBP)		179
10%		220
50%		281
90%		344
Final boiling point (FBP)		367
Gross heating value	cal g^−1	10900	—	IP 12
(b) Fuel properties of the biodiesel used in the Golf vehicle
Property	Units	Biodiesel	EN 14214 limits	Test method
Viscosity, 40°C	mm^2 s^–1	4.4	3.5–5.0	EN ISO 3104
Density, 15°C	g cm^–3	0.8816	0.860–0.900	EN ISO 12185
Flash point	°C	166	120 min	EN ISO 3679
Sulfur content	μ g g^–1	2.0	10.0 max	EN ISO 20846
Water content	μ g g^–1	450	500 max	EN ISO 12937
Copper strip corrosion (3 h at 50°C)	Rating	1A	Class 1	EN ISO 2160
CFPP	°C	–7	–5 max	EN 116
Cetane number		52	51 min	EN ISO 5165
Sulfated ash content	%(m/m)	< 0.01	0.02 max	ISO 3987
Oxidation stability, 110°C	Hours	4.6	6 min	EN 14112
Iodine number		122	120 max	EN 14111
Acid value	mg KOH g^–1	0.4	0.50 max	EN 14104
Monoglyceride content	%(m/m)	0.77	0.80 max	EN 14105
Diglyceride content	%(m/m)	0.19	0.20 max	EN 14105
Triglyceride content	%(m/m)	0.11	0.20 max	EN 14105
Free glycerol	%(m/m)	0.05	0.02 max	EN 14106
Total glycerol	%(m/m)	0.23	0.25 max	EN 14105
Methanol content	%(m/m)	0.12	0.20 max	EN 14110
Ester content	%(m/m)	96.6	96.5 min
Linolenic acid methyl ester	%(m/m)	5.77	12 max
Group I Metals (Na+K)	μ g g^–1	< 0.01, 0.9	5.0 max	EN 14108
				EN 14109
Phosphorous content	μ g g^–1	5	10 max	EN 14107
Gross heating value	cal g^–1	9228	—	IP 12

FIG. 1 Emission factors (ng/km) of 12 priority polycyclic aromatic hydrocarbons (PAHs) classified by the US EPA.

TABLE 2 (a) Emission factors of PM mass (mg/km), elemental carbon (mg/km), organic carbon (mg/km), and sulfate (mg/km). (b) Emission factors of selected trace elements and metals (ng/km)

	Accord diesel	DPF-Accord	Corolla gasoline	Golf diesel	Golf biodiesel
a
PM Mass*	27.13	0.63	2.41	72.08	41.20
Elemental carbon*	19.6 ± 0.5	0.03 ± 0.01	0.05 ± 0.01	39.1 ± 1.08	6.73 ± 0.19
Organic carbon*	4.92 ± 0.14	0.51 ± 0.03	0.95 ± 0.04	24.2 ± 0.6	24.4 ± 0.6
Sulfate*	0.07 ± 0.01	0.1 ± 0.01	0.99 ± 0.05	0.14 ± 0.01	0.26 ± 0.01
b
Al	148 ± 43	20.6 ± 12.3	21.1 ± 12.8	1,160 ± 38	83.1 ± 27.2
Ca	15,100 ± 1,340	BDL	29,700 ± 742	118,000 ± 2,080	54,200 ± 1,740
Fe	5.23 ± 20.5	10.0 ± 8.6	622 ± 10	618 ± 17	428 ± 19
Mg	5,100 ± 127	260 ± 45	1,590 ± 69	4,740 ± 140	8,200 ± 176
Na	17,700 ± 566	BDL	4,760 ± 160	25,300 ± 356	149,000 ± 2,650
P	4,590 ± 148	254 ± 49	3,670 ± 56	31,800 ± 682	29,900 ± 604
S	24,500 ± 1,460	30,800 ± 1,170	301,000 ± 6,350	81,400 ± 1,660	78,000 ± 1,130
K	10,300 ± 581	BDL	4,050 ± 298	13,500 ± 953	524,000 ± 28,600
V	37.8 ± 2.9	BDL	5.26 ± 0.84	27.3 ± 1.6	47.2 ± 2.1
Cr	341 ± 7	67.6 ± 4.6	46.4 ± 6.5	245 ± 7	247 ± 8
Mn	124 ± 24	35.3 ± 11.2	1,640 ± 16	426 ± 23	432 ± 23
Co	5.78 ± 0.70	2.85 ± 0.69	17.5 ± 0.5	23.2 ± 0.9	64.8 ± 1.8
Ni	160 ± 21	104 ± 10	158 ± 10	196 ± 21	59.2 ± 18.7
Cu	BDL	BDL	708 ± 8	BDL	46.3 ± 11.0
Zn	7,020 ± 164	372 ± 65	2,260 ± 60	22,300 ± 187	22,300 ± 403
Cd	5.23 ± 0.79	0.82 ± 0.28	2.69 ± 0.48	5.53 ± 0.88	4.08 ± 0.96
Ba	142 ± 26	BDL	42.1 ± 10.0	185 ± 21	199 ± 19
Pb	18.2 ± 0.8	2.39 ± 0.35	27.9 ± 0.4	247 ± 2	14.1 ± 0.7

TABLE 3 Emission factors (μg/km) of PAHs, hopanes, steranes, alkanes, and organic acid (OA)

	Accord diesel	DPF-Accord	Corolla gasoline	Golf diesel	Golf biodiesel
Σ PAHs	2.55 ± 0.43	BDL	0.67 ± 0.08	16.5 ± 1.4	10.4 ± 0.9
Σ PAHs, MW ≤ 228	2.25 ± 0.43	BDL	0.20 ± 0.05	15.6 ± 1.4	7.76 ± 0.90
Σ PAHs, MW = 252	BDL	BDL	0.22 ± 0.04	0.90 ± 0.16	1.34 ± 0.19
Σ PAHs, MW ≥ 276	BDL	BDL	0.25 ± 0.04	BDL	1.34 ± 0.2
Σ Hopanes	0.94 ± 0.15	0.01 ± 0.02	0.09 ± 0.03	67.9 ± 5.5	59.5 ± 4.8
Σ Steranes	BDL	BDL	BDL	23 ± 1.9	20.2 ± 1.6
Σ Alkanes	197 ± 30	6.95 ± 5.34	9.78 ± 3.09	981 ± 84	125 ± 27
Σ Organics acids	1.04 ± 3.74	6.67 ± 4.84	7.13 ± 4.95	342 ± 43	5,240 ± 355
Σ OA, C9-14	BDL	1.32 ± 1.12	1.71 ± 1.33	11.3 ± 5.0	17.7 ± 6.3
Σ OA, C15-29	1.04 ± 3.74	5.35 ± 4.70	5.42 ± 4.77	331 ± 43	5,220 ± 354

FIG. 2 Emission factors (ng/km) of hopanes and steranes.

FIG. 3 Emission factors (ng/km) of selected n-alkanes.

FIG. 4 Emission factors (ng/km) of selected organic acids.

FIG. 5 DPF removal rates (%) of selected trace elements and metals, selected PAHs, elemental carbon, organic carbon, and water soluble organic carbon of the Honda Accord vehicle.

TABLE 4 Correlations coefficients, R, among selected PM chemical constituents

	Mg	A1	P	S	K	Ca	V	Cr	Mn	Fe	Co	Ni	Zn	Cd	Ba	Pb	ΣPAHs	ΣPAHs, MW ≤ 228	ΣPAHs, MW = 252	Σ Hopanes	Σ Alkanes	Σ Organic acids	Σ OA, C9–14	Σ OA, C15–29
Na	0.84	−0.10	0.68	−0.17	0.99	0.26	0.75	0.38	−0.12	0.21	0.96	−0.70	0.71	0.27	0.67	−0.13	0.46	0.35	0.85	0.64	−0.05	0.99	0.87	0.99
Mg		0.21	0.76	−0.29	0.77	0.46	0.98	0.79	−0.22	0.20	0.79	−0.28	0.84	0.73	0.94	0.15	0.64	0.57	0.77	0.70	0.28	0.77	0.77	0.77
Al			0.66	−0.16	-0.21	0.90	0.19	0.35	−0.14	0.47	0.02	0.64	0.63	0.61	0.52	0.99	0.84	0.90	0.39	0.69	1.00	−0.17	0.36	−0.17
P				−0.16	0.59	0.88	0.65	0.46	−0.11	0.58	0.76	−0.05	0.99	0.62	0.86	0.64	0.96	0.92	0.94	0.99	0.69	0.62	0.93	0.62
S					-0.13	0.04	−0.04	−0.59	1.00	0.69	0.06	0.22	−0.24	−0.18	−0.30	−0.04	−0.21	−0.23	−0.04	−0.19	−0.21	−0.13	−0.13	−0.13
K						0.15	0.66	0.27	−0.09	0.17	0.95	−0.78	0.61	0.14	0.56	−0.24	0.35	0.23	0.80	0.56	−0.17	1.00	0.82	1.00
Ca							0.37	0.33	0.07	0.72	0.41	0.41	0.84	0.66	0.70	0.92	0.95	0.96	0.71	0.88	0.91	0.19	0.66	0.19
V								0.89	−0.33	0.04	0.65	−0.21	0.76	0.78	0.93	0.11	0.56	0.51	0.64	0.59	0.27	0.66	0.63	0.66
Cr									−0.52	−0.19	0.24	0.12	0.59	0.86	0.83	0.25	0.50	0.50	0.31	0.41	0.43	0.27	0.32	0.27
Mn										0.72	0.11	0.23	−0.19	−0.11	−0.22	−0.02	−0.17	−0.19	0.01	−0.15	−0.18	−0.09	−0.09	−0.09
Fe											0.47	0.28	0.49	0.29	0.32	0.56	0.55	0.53	0.59	0.56	0.44	0.20	0.50	0.20
Co												−0.58	0.76	0.28	0.66	0.02	0.55	0.44	0.93	0.72	0.05	0.96	0.92	0.96
Ni													−0.06	0.45	0.03	0.67	0.19	0.30	−0.33	−0.05	0.62	−0.76	−0.40	−0.76
Zn														0.70	0.92	0.59	0.95	0.91	0.92	0.97	0.67	0.65	0.91	0.64
Cd															0.88	0.57	0.69	0.70	0.43	0.56	0.68	0.15	0.38	0.15
Ba																0.47	0.82	0.79	0.77	0.81	0.59	0.58	0.75	0.57
Pb																	0.82	0.88	0.38	0.67	0.98	−0.20	0.34	−0.20
ΣPAHs																		0.99	0.82	0.97	0.86	0.39	0.80	0.39
ΣPAHs,																			0.74	0.93	0.92	0.28	0.72	0.28
MW ≤ 228
ΣPAHs,																				0.93	0.41	0.82	0.99	0.82
MW = 252
ΣHopanes																					0.71	0.60	0.92	0.59
ΣAlkanes																						−0.13	0.38	−0.13
ΣOrganic																							0.85	1.00
acids
ΣOA,																								0.85
C9–14
ΣOA,
C15–29

TABLE 5 DTT consumption rates (nmol/min × km) and ROS activity (μ g of Zymosan units/km)

	Accord diesel	DPF-Accord	Corolla gasoline	Golf diesel	Golf biodiesel
DTT consumption*	624 ± 54	12.0 ± 1.3	29.1 ± 2.4	1300 ± 216	1040 ± 124
ROS activity	BDL	BDL	20.1 ± 1.5	17.7 ± 2.7	10.2 ± 2.4

TABLE 6 Pearson correlation coefficients (R), corresponding significance levels (P), regression slopes (m) (μ g of Zymosan units/ng) or [nmol/(min × ng)], and y-intercepts (b) (μ g of Zymosan units/km) or [nmol/(min × km)] between ROS activity (μ g of Zymosan units/km), DTT consumption rates [nmol/(min × km)], and selected elemental species (ng/km)

	Al	Ca	Fe	K	Mg	Na	P	S	V	Cr	Mn	Co	Ni	Zn	Cd	Ba	Pb	ROS
ROS
R	0.43	0.66	0.99	0.04	0.07	0.08	0.46	0.77	−0.07	−0.27	0.79	0.35	0.37	0.36	0.24	0.21	0.53
P	0.47	0.23	< 0.01	0.99	0.91	0.90	0.44	0.13	0.91	0.66	0.11	0.57	0.55	0.55	0.70	0.73	0.35
m	8.36	0.13	30.2	0.00	0.22	0.01	0.28	0.06	−34.2	−20.1	11.6	133	64.6	0.32	1150	22.6	48.6
b	7.20	3.74	−0.57	9.40	8.70	9.14	5.65	2.94	10.4	13.4	3.40	6.56	0.86	6.13	5.37	7.03	6.58
DTT
R	0.72	0.83	0.36	0.44	0.82	0.56	0.92	−0.37	0.79	0.75	−0.31	0.57	0.12	0.96	0.83	0.95	0.67	0.24
P	0.17	0.08	0.56	0.46	0.09	0.33	0.03	0.54	0.11	0.15	0.61	0.31	0.85	0.01	0.08	0.01	0.22	0.69
m	859	10.5	670	1.11	152	5.24	34.8	−1.91	22631	3420	−282	13354	1299	52.2	248386	6285	3746	15.0
b	355	146	375	479	−5.0	395	112	798	69.4	−46.3	751	296	425	34.9	−310	−113	396	457.5

TABLE 7 Pearson correlation coefficients (R), corresponding significance levels (P), regression slopes (m) [nmol/(min × μ g)] or (μ g of Zymosan units/μ g), and y-intercepts (b) [nmol/(min × km)] or (μ g of Zymosan units/km) between DTT consumption rates [nmol/(min × km)], ROS activity (μ g of Zymosan units/km), and selected organic species (μ g/km)

	Σ PAHs	Σ PAHs, MW ≤ 228	Σ PAHs, MW = 252	Σ Hopanes	Σ Alkanes	Σ Organic acids	Σ OA, C9–14	Σ OA, C15–29	DTT
DTT
R	0.94	0.93	0.78	0.91	0.77	0.47	0.77	0.47
P	0.02	0.02	0.12	0.03	0.13	0.42	0.13	0.42
m	76.9	82.3	757	15.2	1.10	0.12	57.8	0.12
b	142	172	228	212	311	468	231	469
ROS
R	0.45	0.43	0.46	0.44	0.40	0.07	0.37	0.07	0.24
P	0.45	0.46	0.44	0.46	0.51	0.91	0.55	0.91	0.69
m	0.60	0.63	7.22	0.12	0.01	0.00	0.45	0.00	0.00
b	6.03	6.33	6.04	6.53	7.16	9.27	6.73	9.28	7.21

Cheung , K. L. , Polidori , A. , Ntziachristos , L. , Tzamkiozis , T. , Samaras , Z. , Cassee , F. R. , Gerlofs , M. and Sioutas , C. 2009 . Chemical Characteristics and Oxidative Potential of Particulate Matter Emissions from Gasoline, Diesel, and Biodiesel Cars . Environ. Sci. Technol. , 43 : 6334 – 6340 .

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