Interlaboratory Comparison of Quantifying Hydrocarbons and Trace Elements in Sediment Samples from a Tropical Estuary

Nudi, Adriana H.; Wagener, Angela; Gabardo, Irene T.; Lourenço, Rafael A.; Scofield, Arthur

doi:10.5935/0103-5053.20140280

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Articles • J. Braz. Chem. Soc. 26 (2) • Feb 2015 • https://doi.org/10.5935/0103-5053.20140280 copy

Interlaboratory Comparison of Quantifying Hydrocarbons and Trace Elements in Sediment Samples from a Tropical Estuary

Authorship SCIMAGO INSTITUTIONS RANKINGS

The Marine and Environmental Studies Laboratory at PUC-Rio, in partnership with the PETROBRAS R&D Center (Brazil), conducted an interlaboratory comparison of aliphatic and aromatic hydrocarbons and trace element determinations. The goal of this study was to produce a homogeneous and stable material and obtain consensus concentration values for its use as a reference material (RM) for sediments from tropical regions. The prepared material is adequate for use as a reference material because it has remained stable (Test F, ANOVA, p < 0.05) since its preparation in 2007. In this study, several alkylated polycyclic aromatic hydrocarbon (PAH) compounds were included, and the resulting dispersion was the same order of magnitude as the parental PAH (16 PAH USEPA).

reference material; interlaboratory study; petroleum hydrocarbon; trace elements

Bottle × analyte	Mg	Al	Mn	Fe	Cu	Ba	Ti	Pb
Mean	11839	25273	616	30802	50	142	45	4365
SD	201.6	422.3	10.3	516.6	1.1	1.7	0.5	82.9
SED 012	12379	26283	644	32143	50	141	45	4332
SED 014	11857	25237	617	30961	51	140	46	4334
SED 091	11746	25012	614	30647	51	141	45	4311
SED 115	11912	25389	620	31027	52	141	45	4333
SED 134	11996	25422	627	31250	49	141	45	4390
SED 204	11913	25727	618	30924	49	142	46	4522
SED 212	11746	25392	612	30665	49	145	45	4340
SED 259	11700	25040	608	30392	50	145	46	4240
SED 343	11591	25008	604	30263	49	144	45	4300
SED 344	11863	25392	615	30750	51	141	45	4540
SED 347	11832	25172	617	30795	52	143	46	4371
SED 453	11601	24551	604	30068	50	142	45	4361
SED 493	11767	24920	614	30537	51	140	45	4368

Bottle × analyte	SED 30	SED 91	SED 139	SED 204	SED 259	SED 343	SED 374	SED 453	SED 508	SED 551	Mean	SD
N	3.5	2.3	3.5	4.5	2.9	6.9	4.7	4.9	3.4	3.3	4.0	1.3
Acen	20.9	17.7	24.3	21.3	22.2	23.5	25.2	19.8	16.1	17.1	20.8	3.1
Ace	2.8	1.7	3.0	4.4	2.6	3.0	3.5	2.8	2.1	2.6	2.8	0.7
F	11.4	9.6	12.6	14.6	14.9	17.0	15.6	14.2	11.5	11.0	13.2	2.4
Ph	26.0	24.8	27.9	28.0	28.5	31.2	39.0	30.5	28.0	21.6	28.5	4.6
Ant	17.7	17.3	19.4	20.1	21.0	22.8	22.3	21.2	18.8	14.7	19.5	2.5
Fl	52.0	46.5	59.8	47.6	49.3	49.5	62.0	46.0	38.3	40.3	49.1	7.5
Ch	143.3	142.6	165.2	164.6	168.6	173.0	173.6	142.4	124.0	113.8	151.1	21.1
P	122.6	129.8	140.4	144.5	147.5	152.2	149.1	132.7	128.6	85.1	133.2	19.6
BaP	183.3	163.2	221.4	158.1	190.8	193.7	222.0	148.8	131.3	141.4	175.4	31.9
BaAnt	105.0	98.1	121.0	129.9	131.3	138.7	130.1	114.5	97.4	76.9	114.3	19.6
BbFl	213.5	207.2	261.5	211.4	210.8	251.8	264.0	187.7	163.2	148.3	211.9	39.2
BkFl	65.1	57.8	78.1	71.5	71.3	82.9	82.3	59.7	52.2	48.1	66.9	12.3
IP	89.7	77.5	106.6	85.3	91.0	92.2	108.6	70.1	71.0	62.0	85.4	15.4
DBAnt	41.8	35.9	50.1	39.7	45.7	41.4	50.3	31.6	33.5	29.3	39.9	7.4
BghiPe	102.3	87.1	121.4	98.5	104.7	106.3	124.0	80.4	81.6	64.0	97.0	18.8
Pe	70.0	57.5	84.4	74.2	77.2	86.1	90.6	61.0	54.3	59.4	71.5	13.1

Data analyses	Apr 07 (n = 10)	May 07 (n = 5)	Aug 07 (n = 10)	Sep 07 (n = 5)	Aug 08 (n = 5)	Feb 11 (n = 3)	Sep 12 (n = 3)	Oct 12 (n = 3)	Jan 13 (n = 10)	Jan 14 (n = 3)	Mean	SD
Acen	23.2	31.5	22.9	22.5	24.5	18.0	19.9	18.3	27.7	19.2	22.8	4.3
DBT	9.3	11.3	9.2	9.0	9.7	6.1	8.0	8.6	8.2	6.4	8.6	1.5
Ph	31.3	38.3	31.2	35.4	29.7	27.9	26.8	35.4	33.8	29.0	31.9	3.7
Ant	21.4	27.0	21.4	20.0	18.6	12.8	13.5	12.2	16.9	16.0	18.0	4.6
Fl	54.9	69.1	54.2	69.6	51.9	74.3	64.1	72.1	82.7	69.3	66.2	9.9
P	145.9	164.0	145.9	144.6	160.9	122.1	139.5	169.6	106.8	153.0	145.2	19.1
BaAnt	125.7	144.2	124.7	123.7	119.9	82.7	81.8	66.1	91.3	76.0	103.6	26.8
Ch	167.0	215.3	166.4	189.1	175.8	114.3	44.5	49.9	59.0	109.0	129.0	62.4
BbFl	236.1	276.2	231.0	297.8	195.1	129.6	117.1	161.8	153.2	93.1	189.1	69.4
BkFl	74.3	92.5	73.1	74.8	54.5	62.2	37.9	48.8	78.0	38.4	63.5	18.2
BeP	149.8	198.0	146.5	187.9	206.7	131.4	119.7	185.6	136.5	138.1	160.0	31.3
BaP	196.0	259.7	192.5	276.0	178.7	108.2	82.3	98.0	107.1	146.2	164.5	67.9
Pe	79.7	108.6	78.6	98.0	57.9	62.0	38.0	35.6	59.0	18.7	63.6	28.3
IP	95.1	117.9	93.9	134.0	115.3	117.2	76.0	89.1	75.1	94.6	100.8	19.4
DBAnt	44.3	56.6	44.0	52.7	56.2	59.2	37.3	53.7	38.6	47.8	49.0	7.8
BghiPe	107.7	128.4	106.7	126.7	128.4	112.7	75.7	105.6	71.9	100.1	106.4	20.0

Methods	Laboratory code numbers
Extraction method
Soxhlet	2^a a Laboratory that performed the determination using two methods. ASE: accelerated solvent extraction; HPLC: high-performance liquid chromatography; GC-FID: gas chromatography-flame ionization detector. ; 11; 13; 14; 15; 16; 17; 19
Microwave	3
Ultrasound	4; 5; 6; 7; 8; 9; 10
ASE	1; 2
Not indicated	12; 18
Solvents used
Methanol/dichloromethane	5; 6
Dichloromethane	1; 2; 2^a a Laboratory that performed the determination using two methods. ASE: accelerated solvent extraction; HPLC: high-performance liquid chromatography; GC-FID: gas chromatography-flame ionization detector. ; 9; 10; 12; 14; 16; 19
Hexane/acetone	8; 13; 17
Hexane/toluene	4
Hexane/dichloromethane	3; 7; 11; 15
Cyclohexane/dichloromethane	18
Duration of extraction
10 to 30 min	2; 6
4 to 8 h	2^a a Laboratory that performed the determination using two methods. ASE: accelerated solvent extraction; HPLC: high-performance liquid chromatography; GC-FID: gas chromatography-flame ionization detector. ; 11; 16; 17
24 h	14; 19
Not indicated	1; 3; 4; 5; 7; 8; 9; 10; 12; 13; 15; 18
Internal standards
Mixture of deuterated PAH	All participants
Clean-up and/or fractionation of extracts
Saponification/Si-Al	6; 19
Silica/alumina	1; 2; 2^a a Laboratory that performed the determination using two methods. ASE: accelerated solvent extraction; HPLC: high-performance liquid chromatography; GC-FID: gas chromatography-flame ionization detector. ; 8; 11; 12; 13; 17
Treatment with copper/Si-Al	3; 14; 15; 16
Florisil or HPLC	5; 18
None	7; 9; 10
Confirmation of identities
GC-MS (polycyclic aromatic hydrocarbon)	All participants
GC-FID (aliphatic compound)

	1.0 mol L^-1 HCl			EPA 3050			EPA 3052
	ICP-OES	AAS	ICP-MS	ICP-OES	AAS	ICP-MS	ICP-OES	AAS	ICP-MS
Mg	10; 13	17	-	7; 9; 10; 13; 24; 25; 26	16; 17; 18	-	10; 13	17	-
Al	10; 13	17	-	7; 9; 10; 13; 24; 25; 26	16; 17; 18	-	10; 13	17	-
Ca	10; 13	17	-	7; 9; 10; 13; 24; 25; 26	16; 17; 18	-	10; 13	17	-
V	10; 13	-	22	7; 9; 10; 13; 24; 25; 26	16; 18	21; 22	10; 13	-	22
Cr	10; 13	17; 20	22	7; 8; 9; 10; 13; 24; 25; 26	16; 17; 18; 20	21; 22	10; 13	17; 20	22
Mn	10; 13	17	22	7; 8; 9; 10; 13; 24; 25; 26	16; 17; 18	21; 22	10; 13	17	22
Fe	10; 13	17	22	7; 8; 9; 10; 13; 24; 25; 26	16; 17; 18	21	10; 13	17	22
Co	10; 13	-	22	7; 8; 9; 10; 13; 24; 25; 26	16	21; 22	10; 13	-	22
Ni	8; 10; 13	-	22	7; 8; 9; 10; 13; 24; 25; 26	16; 18	21; 22	8; 10; 13	-	22
Cu	8; 10; 13	17; 20	22	7; 8; 9; 10; 13; 24; 25; 26	16; 17; 18; 20	21; 22	8; 10; 13	17; 20	22
Zn	8; 10; 13	17; 20	22	7; 8; 9; 10; 13; 24; 25; 26	16; 17; 18; 20	21; 22	8; 10; 13	17; 20	22
As	10; 13	-	22	7; 9; 10; 13; 24; 26	-	21; 22	10; 13	-	22
Se	10; 13	-	-	7; 9; 10; 13; 24; 26	-	21	10; 13	-	-
Sr	10; 13	-	-	7; 9; 10; 13; 24; 25; 26	-	21	10; 13	-	-
Ag	10	-	22	7; 9; 10; 24; 25; 26	16	22	10	-	22
Cd	10; 13	-	22	7; 9; 10; 24; 26	16	21; 22	10; 13	-	22
Sn	10; 13	-	22	7; 9; 10; 13; 24; 26	16	22	10; 13	-	22
Sb	10; 13	-	22	7; 9; 10; 13; 24; 26	16	22	10; 13	-	22
Ba	10; 13	-	22	7; 8; 9; 10; 13; 24; 25; 26	16; 18	21; 22	10; 13	-	22
Hg	-	-	-	7; 9; 25; 26	-	-	-	-	-
Tl	10; 13	-	22	9; 10; 13; 26	18	22	10; 13	-	22
Pb	8; 10; 13	17	22	7; 8; 9; 10; 13; 24; 25; 26	16; 17; 18	21; 22	8; 10; 13	17	22

Aliphatic hydrocarbons	Average value^a a Average values are expressed on a dry weight basis;	SD^b b standard deviation;	SD / %	N^c c number of accepted laboratory means that were used for calculating the recommended values and the standard deviation.	Outlier / %	Class
C12	141.0	110.7	79	7	30	C
C13	131.2	46.2	35	8	20	C
C14	177.1	61.9	35	11	-	B
C15	198.9	58.5	29	11	-	B
C16	178.7	69.8	39	13	-	C
C17	316.2	74.9	24	12	8	B
Pristane	179.1	67.3	38	11	8	B
C18	265.7	96.8	36	12	8	B
Phytane	244.6	111.0	45	12	8	B
C19	312.3	117.6	38	11	8	B
C20	338.3	135.1	40	13	-	B
C21	462.7	148.6	32	13	-	B
C22	479.0	199.4	42	13	-	B
C23	1128.9	353.1	31	13	-	B
C24	675.7	255.1	38	13	-	B
C25	2427.3	686.5	28	13	-	B
C26	703.6	298.5	42	13	-	B
C27	2911.0	928.1	32	13	-	B
C28	1035.8	439.2	42	13	-	B
C29	5098.5	1429.4	28	13	-	B
C30	702.0	146.4	21	11	15	B
C31	3144.0	1475.8	47	13	-	B
C32	569.8	291.8	51	13	-	B
C33	1639.5	875.2	53	11	8	B
C34	281.0	147.7	53	9	25	C
C35	666.8	336.7	50	10	9	B
C36	163.7	86.0	53	6	33	C
C37	196.3	114.4	58	8	11	C
C38	131.9	68.0	52	7	13	C
C39	152.5	79.9	52	8	-	C
C40	118.1	76.0	64	7	13	C

Aromatic hydrocarbons	Average value^a a Average values are expressed on a dry weight basis;	SD^b b standard deviation;	SD / %	N^c c number of accepted laboratory means that were used in calculating the recommended values and the standard deviation.	Outlier / %	Class
Naphthalene	21.1	14.6	69	14	18	C
2-Methyl naphthalene	40.9	28.6	70	9	25	B
1-Methyl naphthalene	25.4	14.0	55	9	18	B
C2-Naphthalene	95.5	44.6	47	9	18	B
C3-Naphthalene	80.2	39.4	49	9	18	B
C4-Naphthalene	65.2	37.6	58	9	-	C
Acenaphthylene	22.3	9.1	41	14	22	B
Acenaphthene	4.8	2.1	43	12	20	B
Fluorene	10.7	4.2	39	14	18	B
C1-Fluorene	23.0	12.2	53	7	13	C
C2-Fluorene	55.4	30.9	56	6	14	B
C3-Fluorene	99.3	57.5	58	5	17	C
Dibenzothiophene	11.4	4.7	41	9	18	B
C1-Dibenzothiophene	44.4	24.1	54	8	11	B
C2-Dibenzothiophene	185.5	106.0	57	7	13	B
C3-Dibenzothiophene	287.5	154.5	54	6	25	B
Phenanthrene	35.8	15.2	42	15	21	B
C1-Phenanthrene	78.7	39.0	49	8	11	B
C2-Phenanthrene	126.7	64.9	51	9	10	B
C3-Phenanthrene	247.7	138.7	56	8	20	B
C4-Phenanthrene	330.1	213.8	65	7	22	B
Anthracene	16.1	5.0	31	14	22	B
Fluoranthene	71.2	31.3	44	14	22	B
Pyrene	146.2	58.0	40	15	21	B
C1-Pyrene	329.5	215.8	65	9	18	B
C2-Pyrene	825.9	515.1	62	8	11	B
Benz(a)anthracene	97.4	44.8	46	15	17	B
Chrysene	137.1	70.0	51	15	21	B
C1-Chrysene	471.0	176.5	37	9	10	B
C2-Chrysene	1026.1	663.5	65	9	10	B
Benzo(b)fluoranthene	197.1	109.7	56	14	18	B
Benzo(k)fluoranthene	69.8	43.2	62	13	13	B
Benzo(e)pyrene	264.6	59.0	22	8	20	B
Benzo(a)pyrene	163.0	66.6	41	15	21	B
Perylene	74.5	13.2	18	9	25	B
Indeno(1,2,3-c,d)pyrene	125.2	59.9	48	15	21	B
Dibenz(a,h)anthracene	69.9	33.8	48	14	18	B
Benzo(ghi)perylene	146.4	51.9	35	14	22	B

	1.0 mol L^-1 HCl method					EPA methods 3050B or 3051					EPA method 3052
	Average value^a a Average values are expressed on a dry weight basis;	SD^b b standard deviation;	SD / %	N^c c number of accepted laboratory means that were used in calculating the recommended values and the standard deviation.	Outlier / %	Average value^a a Average values are expressed on a dry weight basis;	SD^b b standard deviation;	SD / %	N^c c number of accepted laboratory means that were used in calculating the recommended values and the standard deviation.	Outlier / %	Average value^a a Average values are expressed on a dry weight basis;	SD^b b standard deviation;	SD / %	N^c c number of accepted laboratory means that were used in calculating the recommended values and the standard deviation.	Outlier / %
Mg	8576	3211	37	6	-	11319	3244	29	11	-	11338	1716	15	4	-
Al	7904	4936	62	6	-	35916	14135	39	11	-	64789	7314	11	5	-
Ca	5435	1925	35	5	-	5481	3075	56	10	-	7561	623	8	4	-
V	20.9	14.9	71	5	-	48.7	13.7	28	9	-	69.5	9.1	13	5	17
Cr	44.6	37.3	84	7	-	66.1	13.5	20	14	-	85.7	22.7	26	8	-
Mn	395.1	86.0	22	7	-	572.5	74.3	13	13	-	607.6	114.7	19	6	-
Fe	18739	10833	58	8	-	33519	5154	15	13	7	38146	3803	10	7	-
Co	3.4	2.8	83	7	-	6.5	2.0	30	11	-	11.2	3.7	33	6	-
Ni	8.6	4.5	53	7	-	18.6	3.8	20	11	-	24.0	3.8	16	5	-
Cu	25.4	15.1	59	9	-	47.9	7.3	15	12	8	54.3	8.7	16	6	14
Zn	123.4	46.3	38	10	-	152.8	21.3	14	14	7	183.4	25.0	14	8	-
As	4.3	2.6	60	6	-	6.2	3.3	53	8	11	9.4	2.4	26	6	14
Cd	0.4	0.2	40	4	20	0.9	0.7	74	8	-	-	-	-	-	-
Ba	23.7	16.4	69	6	14	55.4	16.4	30	11	15	236.5	86	36	5	-
Pb	29.9	4.1	14	7	12	37.2	9.2	25	13	-	41.3	4.3	10	4	-

Compound	NIST 1941b		SED 001		IAEA-435
Compound	[ ]	SD	[ ]	SD	[ ]	SD
Naphthalene	848	95	21	14	7.8	6
Fluorene	85	15	11	4	1.6	1
Phenanthrene	406	44	36	15	8.4	5
Anthracene	184	18	16	5	7.9	10
Fluoranthene	651	50	71	31	3.9	4
Pyrene	581	39	146	58	11	15
Benz(a)anthracene	335	25	97	45	3.4	4
Chrysene	291	31	137	70	2.8	2.6
Benz(b)fluoranthene	453	21	197	110	1.8	2.1
Benz(k)fluoranthene	225	18	70	43	-	-
Benz(e)pyrene	325	25	265	59	23	28
Benz(a)pyrene	358	17	163	67	26	42
Perylene	397	45	75	13	-	-
Benz(ghi)perylene	307	45	146	52	0.89	0.65
Indeno(1,2,3-c,d)pyrene	341	57	125	60	2.2	2.6

Compound	RM SED 001			NIST 1941b			QA05SED13^a a Marine Sediment XIII.
Compound	[ ]	SD	n	[ ]	SD	n	[ ]	SD	n
2-Methyl naphthalene	41	29	9	276	53	8	223	116	9
1-Methyl naphthalene	25	14	9	127	14	8	98	24	8
C1-Fluorene	23	12	7	-	-	-	-	-	-
C2-Fluorene	55	31	6	-	-	-	-	-	-
C3-Fluorene	99	57	5	-	-	-	-	-	-
C1-Dibenzothiophene	44	24	8	-	-	-	-	-	-
C2-Dibenzothiophene	185	106	7	-	-	-	-	-	-
C3-Dibenzothiophene	288	154	6	-	-	-	-	-	-
C1-Phenanthrene	79	39	8	-	-	-	55	18	9
C2-Phenanthrene	127	64	9	-	-	-	-	-	-
C3-Phenanthrene	248	139	8	-	-	-	-	-	-
C4-Phenanthrene	330	218	7	-	-	-	-	-	-
C1-Pyrene	329	216	9	52	2	-	-	-	-
C2-Pyrene	826	515	8	-	-	-	-	-	-
C1-Chrysene	471	176	9	-	-	-	-	-	-
C2-Chrysene	1026	663	9	-	-	-	-	-	-

Metals	SED 001		NIST 8704		NIST 695		IAEA 433
Metals	[ ]	SD	[ ]	SD	[ ]	SD	[ ]	SD
V	70	9	94.6	4	122	3	160	11
Cr	86	22	-	-	-	-	136	10
Mn	608	114	544	21	-	-	316	16
Co	11	4	13.57	0.43	65.3	2.4	12.9	1.2
Ni	24	4	42.9	3.7	135	2	39.4	3.1
Cu	54	9	-	-	1225	9	30.8	2.6
Zn	183	25	408	15	-	-	101	8
As	9	2	-	-	200	5	18.9	1.8
Ba	236	86	413	13	-	-	268	32

Laboratory	Country	Results for
Analytical Solutions, RJ	Brazil	PAH /metal
Analytical Technology, SP	Brazil	PAH / metal
Bioagri Ambiental, SP	Brazil	PAH / metal
CEDRE	France	PAH
CONECO, FURG, RS	Brazil	PAH
Departamento de Geociências, Universidade de Aveiro	Portugal	PAH / metal
Departamento de Geologia e Recursos Naturais, Unicamp, SP	Brazil	Metal
Fisheries Research Services Marine Laboratory, Aberdeen	Scotland	PAH
Hidroquímica, FURG, RS	Brazil	Metal
Geochemical, MG	Brazil	PAH / metal
IAEA / MEL	Monaco	PAH / metal
Innolab, RJ	Brazil	PAH
Institute of Chemical and Environmental Research (ID / EA), Barcelona	Spain	PAH
Laboratório de Química Orgânica Marinha, Instituto Oceanográfico, USP, SP	Brazil	PAH
Laboratório de Análise por Ativação com Nêutrons, IPEN, SP	Brazil	Metal
Laboratório de Análises Ambientais, UFPR, PR	Brazil	PAH / metal
Laboratório de Biogeoquímica Ambiental / LBGqA, UFSCar, SP	Brazil	PAH / metal
Laboratório de Meio Ambiente, Centro de Tecnologia de Gás, CTGas, RN	Brazil	PAH / metal
Laboratório de Química, CENA USP, Piracicaba, SP	Brazil	Metal
LaGOM, UERJ, RJ	Brazil	PAH
LAQA, Tecpar, PR	Brazil	Metal
LQAO, CENPES-Petrobras, RJ	Brazil	PAH
Laboratório de Estudos Marinhos e Ambientais (LABMAM), PUC-Rio, RJ	Brazil	PAH
Labspectro, PUC-Rio, RJ	Brazil	Metal
SENAI-CIC/CETSAM, Laboratórios Ambientais, PR	Brazil	PAH
UFSC, SC	Brazil	Metal

Sociedade Brasileira de Química Instituto de Química - UNICAMP, Caixa Postal 6154, 13083-970 Campinas SP - Brazil, Tel./FAX.: +55 19 3521-3151 - São Paulo - SP - Brazil
E-mail: office@jbcs.sbq.org.br

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[1] *e-mail: ahn@puc-rio.br