GEXPLO-05390; No of Pages 13

Journal of Geochemical Exploration xxx (2014) xxx–xxx

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/jgeoexp

High variability in geochemical partitioning of iron, manganese and

harmful trace metals in sediments of the mining port of Santa Rosalia,
Baja California Sur, Mexico
Miguel Angel Huerta-Diaz a,⁎, Albino Muñoz-Barbosa a,b, Xose Luis Otero c,
Jacob Valdivieso-Ojeda b, Enrique Crisanto Amaro-Franco b
a
Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Campus Punta Morro, Km. 103 Carr. Tijuana-Ensenada, Ensenada, Baja California CP 22860, Mexico
b
Posgrado en Oceaografía Costera, Facultad de Ciencias Marinas/Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Campus Punta Morro,
Km. 103 Carr. Tijuana-Ensenada, Ensenada, Baja California CP 22860, Mexico
c
Departamento de Edafoloxía e Química Agícola, Facultade de Bioloxía, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Total trace metal concentrations and the HCl-soluble (MeHCl) and pyrite (Mepyr) fractions were evaluated in
Received 17 August 2013 two sediment cores (SR1 and SR2) and mine tailings from the copper mining town of Santa Rosalia (SR), Baja
Accepted 13 May 2014 California Sur, Mexico. MeHCl were significantly different in the two cores (p ≤ 0.001), in particular Cd and Fe
Available online xxxx
in core SR2 were 29 and 1.0x104 times higher than concentrations found in SR1, respectively. These higher
concentrations in core SR2 are likely due to the fact that the core was collected from a navigational channel
Keywords:
Sediment
last dredged between 1931 and 1948. Assuming that the trace metal (Me) reactive fraction (MeRF = MeHCl +
Trace metal Mepyr) is the most labile, then for each ton of dredged harbor sediment, up to 4.5 ± 3.6 kg of CuRF (equivalent
Pyrite to almost 0.5% of Cu on a weight basis) could potentially be exported into the ocean. Since an important portion
Degree of trace metal pyritization of the reactive trace metals are in the Mepyr fraction, as indicated by their high degree of trace metal pyritization
Enrichment factor (DTMP = 100Mepyr/MeRF) values (N 98% for Cu, Fe, Pb, Zn), export outside of the harbor will oxidatively dissolve
Santa Rosalia trace metals and release them into the marine environment. Trace metal enrichments (EFcrust), relative to
Al-normalized Earth's crust values (ECV) ranged from 0.94 ± 0.14 to (11.5 ± 5.6)x102 times the ECV for Ni
and Cd, respectively. These EFcrust values were differentiated into three groups: EF ≈ 1 (Ni, Fe), 10 b EF b 100
(Mn, Co, Pb, Zn), and EF N 100 (Cu, Cd). Copper enrichments are not surprising considering its high
concentrations in the SR mine tailings; however, the higher Cd enrichments (6 to 11 times higher than Cu)
were unexpected. Further analyses of mine tailings showed that the Cd enrichments increased considerably
through ore processing. Concentrations for a number of trace metals in SR sediments are high even when
compared with wastes from mines of other countries, indicating that these sediments essentially should be
treated as mine tailings. Finally, our results show that the distribution of the different trace metals is not the result
of diagenetic processes, but rather the result of input from ore-derived sources.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction trace metals and, eventually, will introduce them into the benthic food
chain (e.g., Burd et al., 2000).
Marine deposition of mine tailings represents an environmental Since 1868, when Cu was discovered in El Boleo, a formation from
problem since they can severely affect benthic infaunal distribution, the Upper Miocene (Christoffersen, 1997; Colleta and Angelier, 1981)
and contaminate water, suspended particulate matter and sediments rich in Cu, Co, Zn and Mn minerals (Conly et al., 2011), Cu mining
with trace metals (Loring and Asmund, 1989). Sediments with high became the main economic activity of Santa Rosalia, a town located on
copper levels (e.g., N4.7 μmol g-1) are associated with consistent faunal the Gulf of California coast of Baja California. Considering that industrial
declines (Burd, 2002), cellular changes in macroalgae (Correa et al., and urban activities are currently minimal, and the aridity of the area
1999) and with reductions in the number of total taxa (Burd et al., precludes agricultural runoff as well as freshwater inputs to the study
2000; Fariña and Castilla, 2001; Lee et al., 2006). Organisms that survive site, this zone is suitable to study the fate of mine wastes in ocean
to the high trace metal concentrations of mine tailings will accumulate waters.
The beach composition in front of the town of Santa Rosalia and the
⁎ Corresponding author. Tel.: +52 646 174 4601x167; fax: +52 646 174 5303. furnace slag blocks of which the breakwaters were made, is essentially
E-mail address: [email protected] (M.A. Huerta-Diaz). the same (Wilson, 1955). Additionally, it has been calculated that

http://dx.doi.org/10.1016/j.gexplo.2014.05.014
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Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
2 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

there are 3x106 tons of furnace slag on land, an unknown quantity 3. Study site
of this mine waste distributed in shore sediments, and close to
1.4x106 tons of mine tailings in scattered dams (Romero Gil, 1991). The town of Santa Rosalia (population close to 12,000) is located on
Depending on the trace metal distribution among the different mineral- the western coast of the Gulf of California, approximately 1000 km
ogical fractions, changes in redox state and/or in diagenetic processes south of the Mexico–US border and 755 km north of Los Cabos,
could transform the mine tailings into a source of trace metals to Baja California Sur (Fig. 1). Since the closing of the mine complex, the
the overlying water (e.g., Dold, 2006; Förstner et al., 1986; Lee et al., main economic activities of the town have been government services,
2006). It is then reasonable to assume that the concentrations of trace fisheries (mainly squid) and small businesses. Precipitation in the area
metals in the sediments within the area encompassed by the harbor is 125 mm y-1, with prevailing winds from the northeast most of the
should be considerably high and mostly associated with sulfides and year, except from July to August, when they blow from the southeast
oxides, which made them more reactive or labile towards accumulation (Arellano-Morales, 1997). Topography of the area, scattered torrential
by biota or the formation or dissolution of other mineral phases. Hence, rains, and scarce vegetation favors runoff and soil erosion, which has
we can assume, to a first approximation, that trace metals associated been occurring intermittently for a long time. The 0.17 km2 artificial
with sediments of the port will probably be affected by oxidative or harbor (API, 2008), located at 27° 20.353′ N and 112° 15.797′ W, has a
reductive dissolution with time and could eventually be released into water depth between 2 and 9 m, with a channel that was periodically
the water column. dredged, at least until 1931 (Romero Gil, 1991) or 1948 (Wilson,
Here, we present the results of analyses of total trace metals in 1955). Dredging was necessary, especially during the rainy season,
sediments from the Santa Rosalia Harbor and calculations of their because the harbor was built on the delta of the Providencia Creek,
enrichment factors. Solid phase speciation of sediments into two frac- the natural discharge of the pluvial waters of the area into the sea.
tions (HCl-soluble and pyrite) were also carried out. These results Once the mine closed, the harbor and docks were used mainly by fishing
could have important implications for the surrounding environment if and recreational boats.
the harbor sediments become remobilized and exported outside of the
harbor. 3.1. Sampling collection

2. Historical setting Two cores (SR1 and SR2; 34 and 32 cm in length, respectively) were
collected by a diver at approximately 9 m depth using polycarbonate
The ore minerals from the El Boleo Formation consist of hydrother- core liners (7.2 cm interior diameter, 50 cm in length) on July 24,
mal sulfides interspersed with Mn oxides and other weathering-related 1996 (Fig. 1). The cores were immediately sliced into individual centi-
metal oxides (Conly et al., 2011). The sulfides (e.g., pyrite, chalcocite, meter sections with a plastic spatula and each section was transferred
chalcopyrite, bornite, carrolite, sphalerite) occur with minor quantities to 50-mL centrifuge polypropylene tubes. The samples were then stored
of other minerals such as malachite, azurite, boleite, pseudoboleite at −20 ºC for later analysis in the laboratory. Additionally, three sam-
and cumengite (Hunter, 2005). According to Conly et al. (2011), the ples of mine slag produced by El Boleo were collected from abandoned
Mn oxides from El Boleo ores have one of the highest combined enrich- piles located on land (“pile” samples) and other three from a waste
ments of Co, Cu, Pb and Zn ever reported (1.5, 11, 17 and 23 wt percent, delivery tower located in the port docks (“tower” samples) (Fig. 1).
respectively). By 1883 more than 60,000 tons of ore containing 20% Results from the analyses of these samples were reported elsewhere
by weight of Cu were shipped to Swansea, England (Romero Gil, (Muñoz-Barbosa and Huerta-Diaz, 2013). It is important to note that
1991), leaving behind 120 tons of mine tailings accumulated in the the prevailing conditions of the Santa Rosalia harbor have not changed
Providencia Creek, which presently passes through the middle of the significantly since the time of sediment sampling and that, therefore,
town of Santa Rosalia. In 1885 the ore beds started to be exploited by our results can still apply to the present harbor conditions.
the French-owned mining company of El Boleo, and by 1886 the first
furnace started working. In 1901, ten 150-ton water jacket furnaces 4. Methodology
capable of processing 2000 tons of mineral in 24 h were operational,
but they were replaced in 1906 by others of higher capacity. The All laboratory materials were washed with P-free detergents, rinsed
furnaces produced high-grade black and matte copper with an average a minimum of three times with tap water, left in 5% HCl for at least 24 h,
content of 99.3% pure Cu and an average recovery of 87.4% (Romero Gil, and then rinsed three times with deionized water (Milli-Q grade).
1991; Wilson, 1955). Sediments were unfrozen and an aliquot was then taken to determine
The 20,627 hectare mining complex comprised the mines the percentages by weight of water and solid of each sample, which
Providencia, Purgatorio and Soledad, located 5, 7 and 11 km from the were determined by drying 1 to 2 g of wet sediment in an oven at
town of Santa Rosalia, respectively. Copper production peaked at approximately 80 °C until a constant weight was obtained. Acid volatile
13,000 tons of pure Cu between 1910 and 1913, and during 9 years sulfide (AVS) was measured with a modification of the method of
(1890–1899) this mining complex was the leading Cu producer of Cornwell and Morse (1987), which involves digestion of wet sediment
Mexico (Romero Gil, 1991). El Boleo Company remained open until with 1 N HCl and precipitating the evolved H2S as ZnS in a zinc acetate
1954, when the Cu deposits became exhausted. However, the mine trap solution. The ZnS was treated with the Cline reagent (Cline, 1969)
continued operating under Mexican management until 1972, when it to colorimetrically measure the H2S concentration at a wavelength of
was definitely closed. Mining activities at the time of high production 670 nm using a UV–vis spectrophotometer Spectronic model Genesys
demanded a port able to receive merchandise from United States and 2. Fe-AVS concentrations were calculated simply by assuming that
to export the mined Cu to Tacoma, Washington, or Europe. The port of the AVS is composed of iron monosulfide (FeS). The detection limit
Santa Rosalia, finished in 1905 (Wilson, 1955), was able to accommo- of the method was 0.04 μM (~ 4 nmol-AVS g- 1 dry sediment) and its
date up to 13-4000 tons sail ships and several steamships that were precision (calculated by determining the absorbance of five replicate
continually arriving with lumber, rails, railway cars, and other goods sulfide standards at various concentration levels) was ±3% at the 95%
for El Boleo mining complex and the town of Santa Rosalia (Romero confidence level. Final AVS concentrations on a dry weight basis were
Gil, 1991). This artificial harbor is enclosed by two breakwaters made calculated from the percentage by weight of sediments determined
of 1500 kg furnace slag blocks, with the largest breakwater measuring earlier.
800 m in length. In this way, a low-energy and little-perturbed marine Total trace metal concentrations (Metot) were obtained from the hot
area where fine grained sediment, furnace slag and mine tailings have digestion of 0.5 g of dry sediment in covered Teflon beakers treated with
been slowly accumulating since 1905, was created. concentrated HNO3, HClO4 and HF according to the method reported by

Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx 3

Fig. 1. Location of Santa Rosalia harbor showing the position of the two collected cores (SR1 and SR2). “Pile” and “Tower” refer to the sites where mine slag samples were collected.

Carignan and Tessier (1988). At the end of the digestion process, all step involving H2SO4 should be added before the HNO3 step. Since
samples were clear and without residues. Certified reference material sediments within the Santa Rosalia Harbor and surrounding beaches
BCSS-1 was used to ascertain the precision and accuracy of the extrac- have a maximum org-C content of 1.06% (Rodriguez-Figueroa, 2004),
tion procedure, with percentage recoveries and precisions ranging we considered that inclusion of the H2SO4 step was not necessary.
from 93 (Fe) to 102% (Pb) and from 1.3 (Fe) to 11% (Cd, Co, Pb), Trace metal concentrations were determined with an atomic absorption
respectively. Wet sediments were subjected to a chemical sequential spectrophotometer Thermo Jarrell Ash model Smith Hieftje 12 with
extraction method developed by Huerta-Diaz and Morse (1990) to background correction.
separate trace metals associated to pyrite. The method involves the Limits of detection (in nmol g-1) for the different trace metals (Me),
digestion at room temperature of 2.5 g of dry sediment (calculated calculated as three times the standard deviation of the procedural
from the percentage by weight of water and solid of each sample) blanks were (total, HCl-soluble and pyrite, respectively): 4.4x103 for
with 20 mL of 1 N HCl (HCl-soluble fraction, which extracts carbonates, Al (total fraction only), 14, 1.2 and 1.2 for Cd, 1.2 x102, 3.1 and 9.6 for
Fe and Mn oxyhydroxides, AVS, and associated trace metals). The Co, 43, 3.6 and 3.3 for Cu, 8.0x102, 14 and 3.6 for Fe, 2.2 x102, 5.5 and
residue from the previous extraction was digested two times (for 7.5 for Mn, 46, 9.4 and 9.4 for Ni, 1.5x102, 9.9 and 12 for Pb, and 31,
1 and 16 h) with 30 mL of 10 M HF (silicate fraction, includes mainly 1.2 and 2.1 for Zn. For practical purposes, all metals associated with
clays). Finally, the resulting residue was digested during 1 h with sediments will be designated as trace metals, independently of their
10 mL of concentrated HNO3 (pyrite fraction, mainly pyrite and concentration level.
associated trace metals). The silicate fraction was discarded, since it is
considered essentially non-reactive in terms of early diagenetic pro- 5. Calculations
cesses. Huerta-Diaz and Morse (1990) demonstrated that their method
efficiently extracted trace metals associated to pyrite, except in sedi- The sum of the HCl-soluble (MeHCl) and pyrite (Mepyr) metal frac-
ments with an organic carbon (org-C) content N3%, where an additional tions were used to calculate the concentration of the so-called reactive

Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
4 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

fraction (MeRF = MeHCl + Mepyr). This fraction represents the labile sedimentary shale rocks reported by Turekian and Wedepohl (1961)
trace metals that can potentially dissolve, transform into other mineral and Li and Schoonmaker (2005) and, (2) using average trace metal
phases, or become incorporated into the biota. For the special case of concentrations of nearshore sediments of the western coast of the
Fe, the ratio (expressed as a percentage) of Fepyr to FeRF represents the Gulf of California reported by Muñoz-Barbosa and Huerta-Diaz (2013).
degree of pyritization (DOP) introduced by Berner (1970): The two types of enrichment factors will be henceforth termed EFcrust
  and EFGoC, respectively. Although it is preferable to use regional back-
Fepyr ground concentrations to calculate enrichment factor values, utilization
DOP ¼  100 ð1Þ
FeRF of crustal values allows comparison with other geographical regions.
Aluminum was chosen for the geochemical normalization of trace
This expression evaluates the percentage of the reactive fraction that metals, since it is a conservative element that is part of the structure
is present as sedimentary pyrite. However, to account for the contribu- of clays and, therefore, is one of the best proxies to represent the clay
tion of AVS to the DOP Boesen and Postma (1988) introduced the term mineral concentration (Kersten and Smedes, 2002) in estuarine and
degree of sufidization (DOS), which can be calculated by using the coastal sediments (e.g., Goldberg et al., 1979; Schropp et al., 1990;
following equation: Summers et al., 1996; Weisberg et al., 2000). Normalization with Al
  has the advantage of compensating sedimentary trace metal concentra-
FeAVS þ Fepyr tions for grain size and mineralogical variability (Birch, 2003; Loring,
DOS ¼  100 ð2Þ
FeRF 1991), there is minimal anthropogenic contamination with Al and,
because it is the second most abundant element in the Earth's crust, it
Where the contribution of the AVS to the reactive fraction is already has a high natural concentration.
included in the FeRF term, since it is extracted in the HCl-soluble fraction.
Similarly to the DOP expression, the concept of degree of trace metal 6. Results and discussion
pyritization (DTMP) was introduced by Huerta-Diaz and Morse (1990,
1992) to evaluate the percentage of the sedimentary reactive trace 6.1. HCl-soluble, pyrite, AVS and reactive fractions
metal that is associated with pyrite:
  Results from the sequential chemical extraction show that there are
Mepyr important statistical differences between cores SR1 and SR2, which are
DTMP ¼  100 ð3Þ
MeRF evident in the correlation coefficients obtained for several trace metal
pairs (Tables S1 and S2 in Supporting Information). While all correla-
Total trace metal concentrations, normalized with a conservative tions were found to be highly significant (p ≤ 0.001) in core SR2, only
element, were used to calculate enrichment factors (EFMe), according three HCl-soluble (11%) and 15 pyrite (54%) fraction trace metal pairs
to: were highly (p ≤ 0.001) to moderately (p ≤ 0.05) significant in core
  SR1. The relatively high association among the different trace metals
Metot
Altot sample associated with the pyrite fraction in core SR2 suggests that this fraction
EF ¼   ð4Þ plays a more important geochemical role than the one played by
Metot
Altot bkg the HCl-soluble fraction. However, in the case of core SR1 both the
HCl-soluble and pyrite fractions appear to play equally important geo-
where (Me/Al)sample represents the Al-normalized concentration of chemistry roles. Average MeHCl concentrations of the two cores for a
the trace metal (Me) in the sediment sample on a molar ratio basis. given trace metal were significantly different (p ≤ 0.001): values of
Background concentrations, represented by (Me/Al)bkg in Eq. (4), the core SR1 ranged from 0.0017 ± 0.0010 to 0.66 ± 0.25 μmol g-1 for
were calculated in two ways: (1) using the average composition of Cd and Mn, respectively, whereas for core SR2 the values ranged from

Table 1
Average values (±one standard deviation) of degrees of pyritization (DOP), degrees of trace metal pyritization (DTMP), enrichment factors (EF) and HCl-soluble, pyrite and total (TF)
fraction concentrations of the two sediment cores (SR1 and SR2) collected in Santa Rosalia harbor. Reactive fraction (RF) represents the sum of the HCl-soluble and pyrite fractions.
Enrichment factors (EFcrust and EFGoC) were calculated using average composition of sedimentary shale rocks (Li and Schoonmaker, 2005; Turekian and Wedepohl, 1961) and average
composition of nearshore sediments from the Gulf of California (Muñoz-Barbosa and Huerta-Diaz, 2013), respectively. Trace metals are ordered in increasing EFcrust value.

Trace metal HCl-soluble fraction Pyrite fraction DOP or DTMP Total fraction EFcrust EFGoC RF/TF (mol%)

(μmol g-1) (%) (μmol g-1) (molar ratio)

Core SR1
Ni 0.0038 ± 0.0044 0.031 ± 0.016 84 ± 26 0.909 ± 0.090 0.94 ± 0.14 4.20 ± 0.63 3.7 ± 1.4
Fe 0.0165 ± 0.0077 60 ± 29 99.96 ± 0.02 789 ± 142 1.11 ± 0.20 2.12 ± 0.39 7.6 ± 3.5
Mn 0.66 ± 0.25 5.3 ± 1.3 88.8 ± 4.3 123 ± 24 9.5 ± 2.3 15.6 ± 3.8 5.0 ± 1.3
Co 0.032 ± 0.010 0.35 ± 0.14 87 ± 14 2.82 ± 0.44 10.5 ± 2.1 31.7 ± 6.5 13.3 ± 4.4
Pb 0.0078 ± 0.0042 0.76 ± 0.23 98.7 ± 1.1 1.54 ± 0.24 19.1 ± 3.8 28.3 ± 5.6 50 ± 12
Zn 0.011 ± 0.011 0.98 ± 0.40 98.0 ± 3.6 29.8 ± 5.2 24.6 ± 5.5 49 ± 11 3.3 ± 1.1
Cu 0.020 ± 0.050 33 ± 12 99.7 ± 1.0 60 ± 16 102 ± 31 (3.02 ± 0.92)x102 54 ± 21
Cd 0.0017 ± 0.0010 0.0051 ± 0.0017 82 ± 15 1.58 ± 0.39 (7.1 ± 2.1)x102 45 ± 14 0.42 ± 0.16
Al – – – (2.50 ± 0.18)x103 – –

Core SR2
Ni 0.376 ± 0.079 0.044 ± 0.032 9.5 ± 5.3 1.00 ± 0.14 1.07 ± 0.15 4.80 ± 0.69 41.6 ± 7.2
Fe 172 ± 20 54 ± 25 22.9 ± 7.8 770 ± 52 1.124 ± 0.076 2.15 ± 0.15 29.3 ± 4.2
Mn 124 ± 34 0.196 ± 0.065 0.158 ± 0.038 141 ± 36 11.3 ± 2.9 18.6 ± 4.8 87.4 ± 7.1
Co 1.96 ± 0.42 0.31 ± 0.23 12.4 ± 6.6 3.12 ± 0.67 12.0 ± 2.7 36.3 ± 8.2 72.4 ± 7.2
Pb 1.19 ± 0.23 0.28 ± 0.13 18.3 ± 5.7 1.75 ± 0.35 22.4 ± 4.5 33.2 ± 6.7 83 ± 9
Zn 21.5 ± 5.7 0.27 ± 0.19 1.13 ± 0.59 31.7 ± 7.4 27.0 ± 6.5 54 ± 13 68.6 ± 5.7
Cu 38 ± 13 17 ± 11 29 ± 13 67 ± 28 118 ± 49 (3.5 ± 1.5)x102 82 ± 6
Cd 0.0331 ± 0.0075 0.0063 ± 0.0020 15.8 ± 1.9 2.5 ± 1.2 (11.5 ± 5.6)x102 73 ± 36 1.73 ± 0.35
Al – – – (2.41 ± 0.15)x103 – –

Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx 5

Table 2 by the availability of Fe (0.0165 ± 0.0077 μmol g-1 in core SR1 versus
Average values of the degree of pyritization (DOP), degree of trace metal pyritization 172 ± 20 μmol g-1 in core SR2; Table 1). In contrast, average concentra-
(DTMP) and HCl-soluble, pyrite, reactive and total fractions of core SR2 relative to those
of SR1 (SR2/SR1) for the different trace metals and fractions analyzed in this study.
tions of Copyr, Fepyr and Nipyr were statistically similar in both cores, with
the other elements showing statistically different (p ≤ 0.001) average
Element HCl-soluble Pyrite Reactive DOP or Total concentrations. Core SR1 pyrite fraction concentrations ranged from
fraction fraction fraction DTMP
0.0051 ± 0.0017 to 60 ± 29 μmol g-1 for Cd and Fe, respectively,
(molar fraction) whereas core SR2 ranged from 0.0063 ± 0.0020 to 54 ± 25 μmol g-1
Cd 29 1.2 6.3 0.19 1.6 for Cd and Fe, respectively (Table 1). The similarities in some of the
Co 61 0.90 6.0 0.14 1.1 pyrite fraction average trace metal concentrations are more noticeable
Cu 1.8x103 0.52 1.7 0.29 1.1 if SR2/SR1 trace metal ratios are used. These ratios were generally
Fe 1.0x104 0.91 3.8 0.23 1.0
Mn 1.9x102 0.037 21 0.0018 1.2
close to unity for Cu, Co, Fe, Cd and Ni (range of 0.52 to 1.4; Table 2).
Ni 99 1.4 12 0.11 1.1 AVS profiles for cores SR1 and SR2 were similar, with maximum
Pb 1.5x102 0.37 1.9 0.19 1.1 AVS values always located between the 1–2 cm depth (18 and
Zn 2.0x103 0.27 22 0.011 1.1 5.8 μmol g-1, respectively, Figs. 2 and 3). AVS concentrations (average
Al – – – – 1.0
of 0.37 ± 0.16 and 0.15 ± 0.06 μmol g-1, respectively, if their 1–2 cm
maximum values are excluded) were always considerably lower than
those of pyrite (60 ± 29 and 54 ± 25 μmol g-1, respectively). Hence,
0.0331 ± 0.0075 to 172 ± 20 μmol g- 1 for Cd and Fe, respectively contribution of AVS to the iron sulfide pool can be considered as
(Table 1). On average, MeHCl concentrations of core SR2 were 29 (Cd) relatively unimportant.
to 1.0x104 (Fe) times the values of core SR1 (Table 2). Particularly Profiles of MeHCl for core SR1 (Fig. 2) showed a slight to rapid
interesting are the results for Fe, which strongly suggest that further decrease with sediment depth for Cd, Co, Cu, Ni, Pb and, to a certain
diagenetic pyrite precipitation in core SR1 is most probably limited extent, Zn, whereas Fe and Mn showed only slight increases with

Fig. 2. Sediment profiles of AVS and of trace metals associated to HCl-soluble (MeHCl) and pyrite (Mepyr) fractions for core SR1. Triangles represent concentrations below their respective
detection limit.

Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
6 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

Fig. 3. Sediment profiles of AVS and of trace metals associated to HCl-soluble (MeHCl) and pyrite (Mepyr) fractions for core SR2. Triangles represent concentrations below their respective
detection limit.

depth (Fig. 2). Core SR2 exhibited more regular trends, with all MeHCl chalcopyrite, bornite, carrolite, sphalerite; Hunter, 2005) and oxides (in
increasing almost steadily with depth (Fig. 3). Trace metals associated the form of Mn oxides; Conly et al., 2011) into the harbor. The sulfides
with the pyrite fraction in core SR1 showed net increases with depth, can be oxidized through sediment resuspension produced by fishing
except in the case of Cd and, perhaps, Mn (Fig. 2). As in the case of and recreational boats that transit and dock in the harbor (Morse,
MeHCl in core SR2, concentrations of Mepyr increased almost steadily 1991), by a change in the vertical position of the redoxcline, or by
with sediment depth (Fig. 3). One common feature of all pyrite fraction dredging activities. Table 2 shows that SR2/SR1 ratios for MeHCl ranged
profiles in core SR2 was the presence of a subsurface peak located at from 29 (Cd) to 1.0x104 (Fe), whereas those for MeRF ranged from only
5.5 cm depth, which is not reflected in the HCl-soluble fraction 1.7 (Cu) to 22 (Zn). Hence, differences in MeRF concentrations between
(Fig. 3). This feature could be a consequence of the occasional rain- the two cores are simply reflecting the observed differences in MeHCl,
storms or hurricanes that pass through the region, which are capable since Mepyr concentrations were relatively similar in both cores
of transporting sizable amounts of materials via the Providencia Creek. (Table 1). These differences have important implications for both, the
These materials are eventually deposited in its delta, which is located degrees of pyritization and the degrees of trace metal pyritization, as
within the harbor (Wilson, 1955). Since approximately 120 tons of will be discussed in Section 6.2.
mine tailings (composed mainly of sulfides and oxides; Conly et al., Similarly to results reported for the Pacific coast of Baja California
2011) were accumulated in this creek during the early mine operations, and the Gulf of Mexico sediments (Nava-López and Huerta-Diaz,
it is reasonable to assume that part of this sulfide ore minerals have 2001), we found a significant relationship (p ≤ 0.05, r2 = 0.62, n = 8)
been transported into the harbor. Moreover, the differences in concen- between the average values of trace metals associated with pyrite and
trations observed between cores SR1 and SR2 could be ascribed to this those associated with the HCl-soluble fraction for core SR2 (Fig. 4). For
process acting on the portion of the harbor that is more influenced by this core, most of the plotted average trace metal data, consisting
the Providencia Creek delta, following the now vanished, harbor only of values falling above their respective detection limits, were
channel. Transport of material by the creek can introduce important located within the 95% confidence level of the linear regression curves
amounts of Cu, Co, Ni, and Zn sulfides (in the form of pyrite, chalcocite, (dashed line in Fig. 4). The significant relationships found between

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sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx 7

of 0.37 ± 0.14 to (18.8 ± 9.5)x102 μg g-1 for Cd and Fe, respectively;

Table 3]. The redistributed metals will then range from (3.7 ± 1.4)
x10- 4 to 1.88 ± 0.95 kg, for Cd and Fe, respectively, for every ton of
wet bulk sediment (Table 3). According to Morse (1994), 20 to over
90% of pyrite bound As, Cu and Hg can be released in less than a day
if this mineral is exposed to oxic seawater. If the reactive fraction
(MeRF = MeHCl + Mepyr) is used as representative of the most labile
trace metals, then dredging will export from 0.040 ± 0.017 (for Zn) to
4.5 ± 3.6 (for Cu) kg of trace metals for each ton of wet bulk sediment
(0.104 ± 0.044 to 11.7 ± 9.3 kg m-3, respectively). The potential
amounts of Zn, Ni, Cd and Mn that can be exported are relatively
low (0.040 ± 0.017 to 0.11 ± 0.10 kg ton-1), but the quantities corre-
sponding to Co, Pb, Fe and Cu could be rather high (0.88 ± 1.0 to
4.5 ± 3.6 kg ton-1; Table 3). Hence, dredging the harbor most probably
would have deleterious effects on benthic organisms, at least in the
coastal zone of Santa Rosalia, given the high trace metal concentrations
present in its sediments (e.g., Johnston, 1981; Lewis et al., 2001). Finally,
it is important to mention that Cu, which as we have demonstrated is
extremely abundant in the Santa Rosalia sediments, can denaturate pro-
teins and inactivate enzymes by inhibiting cell metabolism through the
chelation of sulfhydryl groups (Sani et al., 2001). Finally, invertebrate
exposure to this element can result in reduced bioturbation activities,
microbial diversity and activity, and detritus processing (Hunting
et al., 2013).

6.2. DOP, DOS and DTMP

Iron was almost completely pyritized in core SR1, which showed an

average DOP value of 99.96 ± 0.02%, a result of the extremely low FeHCl
concentrations (average of 0.0165 ± 0.0077 μmol g-1) in this sediment
core (Table 1). In contrast to core SR1, moderate to high values of FeHCl
(172 ± 20 μmol g-1) in core SR2 produced more modest DOP values that
ranged from 10.4 to 38.2% (average of 22.9 ± 7.8%; Table 1). The contri-
bution of AVS to the iron sulfide pool in the two cores was negligible,
as reflected in the average DOS values (100.00 ± 0.01 and 23.1 ± 7.7%
for cores SR1 and SR2, respectively), which were essentially equivalent
to the ones obtained with the DOP (99.96 ± 0.02% and 22.9 ± 7.8%
for cores SR1 and SR2, respectively). It is important to note that the
high DOP and DOS values of core SR1 indicate that pyrite production
is limited by the availability of FeHCl in this part of the harbor.
Fig. 4. Average concentrations (±one standard deviation) of trace metals associated Huerta-Diaz and Morse (1992) reported that Co, Cu, Mn and Ni
to HCl-soluble (MeHCl) fraction plotted against those associated to pyrite (Mepyr) for
increased their DTMP values with increasing DOP values in a gradual
cores (a) SR1 and (b) SR2. Linear regression analysis and its 95% confidence level are
represented by the continuous and dashed lines, respectively. Note the logarithmic scale
and almost linear trend and that they were almost equally partitioned
on both axes. between the HCl-soluble and pyrite fractions. A second group of
elements represented by Cd, Pb and Zn was found by Huerta-Diaz and
Morse (1992) to be depleted in the pyrite relative to the reactive frac-
the two fractions simply show that higher concentrations of a given tion. However, the behavior of the degrees of trace metal pyritization
trace metal in the HCl-soluble fraction produce higher concentrations (DTMP) for Gulf of Mexico and Mexican Pacific sediments described
in the pyrite fraction. Core SR1 showed no significant relationship by Huerta-Diaz and Morse (1992) and Nava-López and Huerta-Diaz
between the average values of trace metals associated with pyrite (2001), respectively, were completely different to the one obtained for
and those associated with the HCl-soluble fraction (Fig. 4), a conse- core SR1: absence of gradual increases of DTMP with increasing DOP
quence of, among other factors like redox conditions, the generally values for Co, Cu, Mn and Ni (Fig. 5); almost complete pyritization of
low MeHCl concentrations found in this core (e.g., compare Fig. 4a Cd, Pb and Zn (range of 82 ± 15 to 98.7 ± 1.1; Table 1); and generally
with b). high DTMP values, ranging from 82 ± 15 to 99.7 ± 1.0% for Cd and
Changes in the vertical position of the redoxcline, sediment resus- Cu, respectively (Table 1). To our knowledge, similar high DTMP values
pension or dredging activities can have important implications for the have been reported in sediments from Guaymas basin, where fluids rich
geochemical redistribution of trace metals, especially if high concentra- in sulfides and trace metals are vented through hydrothermal chimneys
tions of iron sulfides are present. Pyrite acts as an important sink for a (Otero et al., 2003). Sediments of the euxinic Nordåsvannet fjord in
number of trace metals (e.g., Huerta-Diaz and Morse, 1992) and its western Norway, where sewage input has contributed to the entrap-
exposure to oxic conditions can potentially cause environmental ment of Fe (in the form of pyrite) and associated trace metals, showed
hazards through the remobilization of trace metals to the water column similarly high DTMP values (Müller, 2002). However, our study site pre-
(Jones and Turki, 1997; Morse, 1994; Saulnier and Mucci, 2000). sents inputs of ore minerals and ore processing refuses, which certainly
An approximation of the potential amounts of redistributed trace contribute to its high DTMP and DOP values. Hence, our values are not
metals can be calculated from the average trace metal concentrations the result of diagenetic processes, but rather the result of the input
(on a wet weight basis) associated to pyrite for the two cores [range from the ore-derived sources.

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sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
8 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

Table 3
Average concentrations of pyrite- and reactive-associated trace elements (on a wet weight basis) in sediments of Santa Rosalia harbor. These values were used to calculate the average
amounts of trace metals per ton or cubic meter of wet bulk sediment that can potentially be exported in case the harbor is dredged. For transformation of mass to volume, sediment density
was assumed to be 2.6 g cm-3.

Element Average concentration of SR1 and SR2 Average concentration of SR1 and SR2 Average kg of trace metal exported Average kg of trace metal exported
-1 -1 for each ton of bulk sediment for each m3 of bulk sediment
(μmol g ) (μg g )

Pyrite-associated trace metals

Cd (3.3 ± 1.2)x10-3 0.37 ± 0.14 (3.7 ± 1.4)x10-4 (9.5 ± 3.6)x10-4
Ni (25 ± 14)x10-3 1.46 ± 0.81 (14.6 ± 8.1)x10-4 (38 ± 21)x10-4
Co 0.20 ± 0.11 11.6 ± 6.8 (11.6 ± 6.8)x10-3 (30 ± 18)x10-3
Pb 0.31 ± 0.20 65 ± 42 0.065 ± 0.042 0.17 ± 0.11
Zn 0.38 ± 0.30 25 ± 20 0.025 ± 0.020 0.065 ± 0.051
Mn 1.7 ± 1.6 92 ± 90 0.092 ± 0.090 0.24 ± 0.23
Cu 15.2 ± 8.8 (9.6 ± 5.6)x102 0.96 ± 0.56 2.5 ± 1.5
Fe 34 ± 17 (18.8 ± 9.5)x102 1.88 ± 0.95 4.9 ± 2.5

Reactive-associated trace metals

Ni 0.40 ± 0.42 24 ± 25 0.024 ± 0.025 0.061 ± 0.065
Zn 0.61 ± 0.26 40 ± 17 0.040 ± 0.017 0.104 ± 0.044
Cd 0.61 ± 0.69 69 ± 78 0.069 ± 0.078 0.18 ± 0.20
Mn 1.9 ± 1.8 107 ± 99 0.11 ± 0.10 0.28 ± 0.26
Co 15 ± 18 (8.8 ± 10.5)x102 0.88 ± 1.0 2.3 ± 2.7
Pb 6.1 ± 6.4 (1.3 ± 1.3)x103 1.3 ± 1.3 3.3 ± 3.4
Fe 52 ± 26 (2.9 ± 1.5)x103 2.9 ± 1.5 7.6 ± 3.8
Cu 71 ± 56 (4.5 ± 3.6)x103 4.5 ± 3.6 11.7 ± 9.3

Core SR2 exhibited lower average DTMP values (range of 0.158 ± whereas in the case of Cu for each increase in one percentage point of
0.038 to 29 ± 13% for Mn and Cu, respectively; Table 1) relative to DOP, the DTMP-Cu increases by as much as 1.654 ± 0.087%.
core SR1 (SR2/SR1 values ranging from 0.0018 to 0.29 for Mn and Cu, The two questions that may arise are: (1) Why core SR1 is highly
respectively; Table 2), with DTMP values gradually increasing with in- pyritized whereas SR2 is not? And, (2) Why such high DOP and DTMP
creasing DOP values (Fig. 5). Our results for core SR2 are in agreement values were maintained in core SR1, but not in core SR2? We can spec-
with the ones obtained by Nava-López and Huerta-Diaz (2001) and ulate that, as mentioned in Section 6.1, sulfide and oxide ores were
Huerta-Diaz and Morse (1992) for sediments of the Mexican Pacific delivered to the harbor by the Providencia Creek during storm events
and the Gulf of Mexico, respectively. However, as shown in Fig. 5, and, once in the harbor, they were resuspended by commercial and
DTMP values in core SR2 show significant to highly significant linear recreational vessels. This hypothesis assumes that the delivered ore
correlations (r2 = 0.45 to 0.92, p ≤ 0.01 or better, n = 32) with the preferentially and gradually filled the channel that existed along the
DOP. Since the steeper the slope in Fig. 5 is, the more readily the element harbor and that this channel eventually disappeared when dredging
is pyritized, then the order in which elements are pyritized is Mn b was stopped sometime between 1931 (Romero Gil, 1991) and 1948
Zn b Cd b Ni b Pb b Co b Cu. Hence, according to the slope values (Wilson, 1955). Marine vessels continued passing where the old channel
obtained in Fig. 5, for each increase in one percentage point of DOP, used to be, resuspending and oxidizing sulfides in the sediments in the
the DTMP-Mn in core SR2 increases by only 0.00329 ± 0.00066%, process. This scenario could produce the relatively low DOP and DTMP

Fig. 5. Degrees of pyritization (DOP) plotted against degrees of trace metal pyritization (DTMP) for cores SR1 and SR2. Regressions are represented by the continuous lines.

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sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx 9

values observed in core SR2, assuming this core was located on the Cd, whose more contemporary values were less than 40 times lower
(now disappeared) channel, whereas core SR1 was not. High DOP (range of 0.017–0.056 μmol g-1). These results suggest that cores SR1
and DTMP values were maintained in core SR1 simply because it was and SR2 are still representing the actual conditions of the Santa Rosalia
probably located in a low energy region of the harbor with minimum harbor, except for Cd. We do not know the reason for the considerable
boat traffic or its geochemical conditions promoted the absence of difference in Cd concentrations between our sediments and the more
bioturbation produced by benthic organisms. contemporary samples collected by Shumilin et al. (2013). A possible
explanation could be that Cd was preferentially dissolved as a result of
6.3. Total concentrations weathering processes preferentially affecting an (as yet) unidentified
ore-derived mineral rich in this element, resulting in lower Cd values
Total trace metal profiles show slightly increasing concentrations for modern (surficial) sediments. Interestingly, reported values for
with increasing depth in both cores (Fig. 6), a trend that appears to be samples collected in the sandy beach located in front of Santa Rosalia,
more noticeable for core SR2. The opposite trend was observed for Al, a sedimentary environment less prone to high trace metal concentra-
with values decreasing slightly with sediment depth. With the excep- tions and more prone to weathering than the harbor, were similar
tion of Fe, concentrations in core SR2 showed a heightened increase (0.038 ± 0.011 μmol g-1; Muñoz-Barbosa and Huerta-Diaz, 2013) or
below 23 cm depth; since normalization with Al did not remove these more than three times higher (0.12 μmol g-1; Rodríguez-Meza, 2004)
increases it can be assumed that there is a lithological change below than the average Cd value reported by Shumilin et al. (2013) for the
this depth (Fig. 7). Total concentrations for both cores were very similar harbor (0.035 ± 0.014 μmol g-1). (2) Average total trace metal concen-
for a given element, as shown by the SR2/SR1 ratios, all of which exhib- trations in sediments were generally lower than in mine slags (“tower”
ited values very close to unity (range 1.0 to 1.2), except for Cd whose and “pile” in Fig. 8 and Table 4), except Cu, Ni and Pb (whose values
value was 1.6 (Table 2). The depth distribution for all trace metals ap- were of similar magnitude). (3) Average Co and Cu concentrations in
pears to be independent of grain size because the Al-normalized sediments were similar than those reported for stratiform ore beds
profiles were essentially the same as the total ones. Total concentrations (also called mantos; Conly et al., 2011), Mn and Zn values were slightly
for both cores followed the order Ni b Pb b Co b Cd b Zn b Cu b Mn b Fe lower, and Fe values were considerably higher. Sediment trace metal
and ranged from 0.909 ± 0.090 to (2.50 ± 0.18)x103 μmol g-1for Ni impoverishments suggest dilution of ore minerals by terrestrial or
and Al, respectively (Table 1). biogenic contributions or reworking of the original mantos and mine
It is interesting to note that, according to Fig. 8: (1) surficial sediments slags by weathering processes. Iron enrichment in sediments may
collected in October 2011 by Shumilin et al. (2013) from the Santa indicate trace metal precipitation as sulfides or carbonates. (4) Mineral
Rosalia harbor were similar to our surficial sediment values, except for ore processing resulted in Cd, Co, Fe, Mn and Zn enrichments in mine

Fig. 6. Sediment profiles of total trace metals (Metot) for cores SR1 and SR2.

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sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
10 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

Fig. 7. Sediment profiles of trace metal/aluminum molar ratios (Me/Al) for cores SR1 and SR2.

slags, but the processing had no apparent effect on Cu and Ni, whose Punta Estrella or San Luis Gonzaga Bay (Daesslé et al., 2002), and Ni
concentrations were similar in both, mine slags and mantos (Ni data close to 70 times lower in Mulegé (Shumilin et al., 2001). Copper and
for mantos were not available). Co were close to 20 times higher in Santa Rosalia (Fig. 8) than in La Paz
These findings can be summarized in Fig. 9, where the average (Shumilin et al., 2001) and Mulegé (Shumilin et al., 1996), respectively,
concentrations of ore-derived materials (mantos and mine slags from whereas Zn and Pb were only 2 to 4 times higher than in La Paz
“pile” and “tower”) were plotted against those of the harbor sediments. (Shumilin et al., 2001). In contrast, only Fe showed lower values
Any value located below the identity line (1:1 line shown in Fig. 9) can (approximately one tenth; Fig. 8) in Santa Rosalia when compared
be considered as ore-derived material enrichment, whereas any value with concentrations reported for Mulegé (Shumilin et al., 1996),
above the identity line can be considered as sediment enrichment. It is Puertecitos, San Luis Gonzaga Bay or Punta Estrella (Daesslé et al.,
clear from this figure that Ni, Cu, Fe (except the manto value), Pb 2002). However, the low Fe values in Santa Rosalia relative to other
(only tower value), Co (only manto value) and Al were not subjected sites in the gulf coast of Baja California are consistent with our findings
to large-scale fractionation during the weathering processes (a well- of pyrite formation limited by lack of reactive Fe within the harbor. The
known Al characteristic; Drever, 1988; Schropp et al., 1990; Summers ore mineral influence on the harbor sediments is better appreciated if
et al., 1996), since all these elements fall on, or are very close to, the reactive to total trace metal concentration ratios are used, some of
identity line in both cores. In contrast, Cd, Co, Mn, Pb (only pile value) which are substantial. For example, according to Table 1 on average
and Zn were all located below the identity line, suggesting that more than 50% (68.6 ± 5.7–87.4 ± 7.1%) of the total trace metal
weathering, ore processing and/or sediment dilution (by terrestrial or concentrations of Zn, Co, Cu, Pb and Mn from core SR2 were part of
biogenic particles) had the effect of depleting these elements in the the reactive fraction. For core SR1 there were still some trace metals
sediments of both cores. Iron showed mixed results, with the pile and (Pb, Cu) which showed a considerable percentage (50 ± 12 and 54 ±
tower values positioned very close to the identity line, but with the 21, respectively) of trace metals associated to the reactive fraction
manto value showing considerable enrichment in the sediments, prob- (Table 1).
ably (as mentioned before), due to iron sulfide precipitation (Fig. 9). Concentrations in Santa Rosalia harbor sediments are still higher for
Total trace metal concentrations are undoubtedly influenced by the a number of trace metals when compared with mine wastes from other
mineral ore contributions, as can be seen in Fig. 8, where values from regions (Fig. 8). For example, Co, Mn, Ni, Pb and Cd (except for Black
other sites of the gulf coast of Baja California (La Paz, San Luis Gonzaga Angel mine in Greenland) concentrations were higher than values
Bay, Punta Estrella, Mulegé and Puertecitos; Fig. 1) were compared reported for tailings of the mines of El Salvador in Chile (Besaury
with the average values obtained from cores SR1 and SR2. For example, et al., 2012; Ramirez et al., 2005), Marcopper in Philippines (David,
relative to Santa Rosalia, Cd values are close to 600 times lower in La Paz 2009), Potrerillos-El Salvador in Chile (Dold, 2006) and Black Angel
(Shumilin et al., 2001), Mn more than 100 times lower in Puertecitos, in Greenland (Loring and Asmund, 1989). Only Fe showed lower

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sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx 11

Fig. 8. Average (±one standard deviation) total trace metal concentrations (Metot) for cores SR1, SR2 and mine tailings (“Tower” and “Pile”; Muñoz-Barbosa and Huerta-Diaz, 2013) from
Santa Rosalia compared with reported concentrations from other mines of the world: Cu, Co, Fe, Mn and Zn from stratiform ore beds, or mantos, from El Boleo Formation (Conly et al.,
2011); Cu concentrations from Island Copper Mine (Ruppert Island, British Columbia, Canada; Burd, 2002); Cd, Cu and Zn from Caleta Palito (El Salvador copper mine, Chile; Besaury
et al., 2012); Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn from Marcopper Mine (Marinduque, Island, Philippines; David, 2009); Cu, Ni, Pb and Zn from Chañaral Bay (Potrerillos-El Salvador mining
district, Chile; Dold, 2006); Cd, Pb and Zn from Black Angel mine (Greenland; Loring and Asmund, 1989); Cu, Fe and Zn from an old mine in Parys Mountain (Anglesey Island, North Wales,
England; Parkman et al., 1996); Cd, Cu, Fe, Mn, Ni, Pb and Zn from El Salvador mine tailings (Ramirez et al., 2005). Reported trace metal concentrations are also shown for other regions of
the Gulf of California: Fe and Mn values for San Luis Gonzaga Bay, Puertecitos and Punta Estrella were taken from Daesslé et al. (2002); Cd, Cu, Pb and Zn concentrations from La Paz were
taken from Shumilin et al. (2001); Co, Fe and Ni values from Mulegé were taken from Shumilin et al. (1996). Recent values for surficial sediments from Santa Rosalia were taken from
Shumilin et al. (2013). Symbols connected by a thick continuous line represent trace metal concentration ranges.

concentrations than those reported for the tailings of the mines group, however, included only Cu, with Cd now included in the EFG2GoC
Marcopper, El Salvador and Parys Mountain (England; Parkman et al., group (Fig. S2 in Supporting Information). Cadmium and Cu showed
1996). Copper was the only element for which mine tailing concentra- high enrichment factors independently of the type of concentration
tions from Parys Mountain, El Salvador, Marcopper, Potrerillos-El used as background value (Table 1), an expected result for Cu consider-
Salvador and Island Copper (Canada; Burd, 2002) showed values similar ing the high concentrations of this trace metal in the Santa Rosalia mine
to our sediments (Fig. 8). These few examples show that Santa Rosalia tailings. However, the high enrichments of Cd [45 ± 14 - (7.1 ± 2.1)
total trace metal concentrations are fairly high and that its sediments x102 for EFGoC and EFcrust, respectively] are somewhat surprising since
should be treated as mine tailings. Analysis of these concentrations in Cu [(3.02 ± 0.92)x102 - 102 ± 31 for EFGoC and EFcrust, respectively] is
terms of enrichment factors will further illustrate the magnitude of supposedly the main contaminant in Santa Rosalia. However, since the
the contamination levels of the harbor. EFcrust and EFGoC values for all trace metals in the mine slags (“pile”
and “tower”, Table 4) were always equal or higher than the values
6.4. Enrichment factors (EFcrust and EFGoC) obtained for the harbor sediments (Figs. S1 and S2 in Supporting
Information), the Cd enrichments are probably a consequence of the
Sediment enrichment factor (EFcrust) values, calculated with the ore processing. These enrichments are further enhanced, however,
average composition of sedimentary shale rocks concentrations with the Cd contribution from nearshore sediments, which consistently
(expressed as molar ratios), ranged from 0.94 ± 0.14 (SR1) to (11.5 ± show high enrichment factors along the western coast of the GoC
5.6)x102 (SR2) for Ni and Cd, respectively (Table 1). Based on these (Muñoz-Barbosa and Huerta-Diaz, 2013). Hence, as mentioned in
values, elements were divided into three basic EFcrust groups (Fig. S1 Section 6.3, mineral ore processing resulted in trace metal enrichments
in Supporting Information): The first group (EFG1crust), which included of mine slags which, in turn, enriched the harbor sediments through
Ni and Fe, had EF ≈ 1; the second group (EFG2crust), consisting of Mn, their occasional contributions from the Providencia Creek. However,
Co, Pb and Zn, had 10 b EF b 100; and the third group (EFG3crust), the low EFcrust and EFGoC values of the sediments relative to the slags
which included Cu and Cd, had EF N 100. When the EF values were suggest that weathering, ore processing and/or dilution by terrigenous
calculated with the average composition of nearshore sediments from and biogenic particles took place. Finally, it is important to mention
the Gulf of California (EFGoC), the enrichments were generally higher that the high Cd concentrations and enrichment values measured in
than the ones obtained using the average composition of sedimentary the Santa Rosalia Harbor imply the existence of an unknown refractory
shale rocks (Table 1). EFGoC values ranged from 2.12 ± 0.39 (SR1) to mineral phase resistant to hydrochloric and nitric acids. The most com-
(3.5 ± 1.5)x102 (SR2) for Fe and Cu, respectively, giving enrichments mon Cd mineral is CdS (greenockite and hawleyite), which is readily
that ranged from 0.018 to 0.44 times the EFcrust values for Fe, Cd and dissolved in hydrochloric and nitric acids (i.e., it will be dissolved during
Ni, and from 2.4 to 186 times the EFcrust values for Zn, Co, Mn, Pb and our sequential extraction scheme). Considering that the mined ore min-
Cu (Table 1). Elements ordered according to EFGoC values also formed eral was subjected to high temperatures and that the ore processing
three basic groups similar to the ones obtained with EFcrust. The EFG3GoC produced crystallized slag material as one of the final products, it is

Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
12 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

Table 4
Average total trace metal concentrations and enrichment factors (± one standard
deviation) of mine slags (Muñoz-Barbosa and Huerta-Diaz, 2013) and mantos (Conly
et al., 2011) from El Boleo Mine complex, Santa Rosalía, Baja California Sur. One to three
samples were collected from abandoned piles of mine slags on land (“Pile”) and from a
waste delivery tower (“Tower”) located in the dock of the Port of Santa Rosalía.
Enrichment factors (EFcrust and EFGoC) were calculated using average composition of
sedimentary shale rocks (Li and Schoonmaker, 2005; Turekian and Wedepohl, 1961)
and average composition of nearshore sediments from the Gulf of California (Muñoz-
Barbosa and Huerta-Diaz, 2013), respectively (see text for details).Note: na = not
available.

Trace metal Towera Pilea Mantosb

-1
Total concentration (μmol g )
Cd 105 60 Na
Co 25.5 ± 1.7 14.59 ± 0.49 4.5 ± 2.3
Cu 35 ± 31 106 ± 92 46 ± 32
Fe (1.54 ± 0.11)x103 (1.15 ± 0.12)x103 0.091 ± 0.028
Mn 791 ± 58 1099 ± 44 (3.2 ± 1.4)x102
Ni 1.203 ± 0.082 0.908 ± 0.051 Na
Pb 1.84 ± 0.24 8.60 ± 0.70 Na
Zn 77.2 ± 7.5 101.5 ± 4.8 80 ± 46
Al 2045 ± 92 2274 ± 127 Na

Enrichment factor, EFcrust (molar ratio)

Cd (5.51)x104 (2.88)x104 Na
Co 115 ± 12 59.1 ± 4.0 Na
Cu 106.0 ± 5.0 284 ± 10 Na
Fe 2.64 ± 0.11 1.77 ± 0.10 Na
Mn 74.4 ± 9.0 93.0 ± 9.1 Na
Ni 1.51 ± 0.11 1.025 ± 0.083 Na
Pb 27.8 ± 4.8 116.2 ± 8.2 Na
Zn 77 ± 11 91.5 ± 9.6 Na

Enrichment factor, EFGoC (molar ratio)

Cd (3.50)x103 (1.82)x103 Na
Co 348 ± 37 179 ± 12 Na
Cu 313 ± 15 838 ± 30 Na
Fe 5.04 ± 0.22 3.39 ± 0.19 Na
Mn 122 ± 15 153 ± 15 Na
Ni 6.76 ± 0.50 4.59 ± 0.37 Na
Pb 41.2 ± 7.1 172 ± 12 Na
Zn 155 ± 22 183 ± 19 Na

possible that this crystallized material created a new refractory Cd

mineral phase resistant to hydrochloric and nitric acids. Fig. 9. Average concentrations of total trace metals in ore-derived material (pile,
tower and mantos; see text for explanation) plotted against average total trace metal
concentrations (±one standard deviation) in SR1 and SR2 sediment cores. Black (red),
7. Conclusions gray (yellow) and white (cyan) symbols represent the tower, pile and mantos values,
respectively. Gray (green) continuous lines represent the identity (1:1) line. Note the
log scales in both axes.
(1) Enrichment factors indicate that sediments from Santa Rosalia
harbor are contaminated with Mn, Co, Pb, Zn and severely
contaminated with Cu and Cd.
(2) The high level of sediment contamination was originated from (6) Finally, our results showed significant geochemical differences
mine wastes and slags supplied to the harbor by the Providencia between the two sampling points, whereas total concentrations
Creek. Mineral ore processing further enriched the mine slags were of similar magnitude. These findings are of fundamental
with trace metals, adding even more trace metal contamination importance in aquatic environmental studies in order to carry
to the harbor sediments. out a proper assessment of the mobility and toxicity of toxic
(3) Given the magnitude of trace metal enrichments, dredging of elements.
harbor sediments will export considerable amounts of trace
metals to the open ocean, posing a threat to marine benthic Supplementary data to this article can be found online at http://dx.
organisms. doi.org/10.1016/j.gexplo.2014.05.014.
(4) As a result of the mine waste contributions, composed mainly of
mineral oxides and sulfides, some parts of the harbor show
almost complete pyritization of Fe (99.96 ± 0.02%) and trace Acknowledgments
metals (82 ± 15 to 99.7 ± 1.0% for Cd and Cu, respectively).
This high DOP average value suggests that pyrite production in The authors would like to thank Rafael Blanco-Betancourt for
core SR1 is limited by the availability of FeHCl. collecting the sediment cores. J.V.-O., A.M-B. and E.C.A.-F. benefited
(5) The average values of trace metals associated with pyrite are sig- from a scholarship from Consejo Nacional de Ciencia y Tecnología
nificantly (p ≤ 0.05 or better) correlated with those associated (CONACYT). This research was funded by Universidad Autónoma de
with the HCl-soluble fraction for both cores, indicating that the Baja California grant 4078-5 to M.A.H.-D. We thank two anonymous
magnitude in the concentration in one fraction is determined reviewers and the Associated Editor for their helpful suggestions and
by the magnitude of the other. critical comments.

Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014
 M.A. Huerta-Diaz et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx 13

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Please cite this article as: Huerta-Diaz, M.A., et al., High variability in geochemical partitioning of iron, manganese and harmful trace metals in
sediments of the mining port of Santa ..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.05.014