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Risk Assessment Through Ieubk Model in an

Inhabited Area Contaminated with Lead


M.R. Delgado-Caballero,a M.C. Valles-Arag on ,b R. Millan,c and M.T. Alarc on-Herreraa
a
Advanced Materials Research Center (CIMAV), Miguel de Cervantes 120, Industrial Chihuahua, Chih, Chihuahua 31109, Mexico;
teresa.alarcon@cimav.edu.mx (for correspondence)
b
Autonomous University of Chihuahua, Faculty of Agrotechnological Science, Pascual Orozco and Universidad, Campus I, Chih,
Chihuahua 31200, Mexico
c
Research Center of Energy, Environment and Technology (CIEMAT), Avenida Complutense 40, Madrid 28040, Spain
Published online 00 Month 2017 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12692

Over centuries the mining industry has been accumulat- The chemical forms of metals present in the environment
ing a great quantity of wastes. The main potentially toxic ele- have a major influence on the effects in human beings. The
ments present in the mining wastes are metals and toxicokinetics and the toxicodynamics of the PTE depend on
metalloids. Due to its effects on human health, lead is one of the metal, the compounds with other elements, and the
the metals in wastes of more concern. Children are the most organism’s capacity to regulate and store the metal [4].
vulnerable to inorganic-Pb exposure, due to their behavior Due to the effects on human beings caused by the con-
and physiology. Therefore, the objective of this research was stant exposure to high levels of Pb, the International Agency
to determinate lead concentration and dispersion in an for Research on Cancer has classified inorganic Pb and its
inhabited area, also to estimate the risk for children popula- compounds as probably carcinogenic (group 2A) [5]. Chil-
tion in the site through the model IEUBK (Integrated Expo- dren are most vulnerable to the exposure to Pb, due to their
sure Uptake Biokinetic model). The inorganic lead in dust behavior and physiology [6].
present in the inhabited area was analytically determined. In order to know the risk caused by the pollutants pre-
The risk assessment of lead exposure for children, predicted sent in a site, an evaluation of environmental risk must be
that is a probability from 31.68 to 90.61% of have lead in done. Mexican regulation NOM-147-SEMARNAT/SSA1 estab-
blood above of 10 lg dL21. Remediation actions are recom- lishes the criteria to determine the maximum permissible lev-
mended in order to mitigate the population exposure. A risk els of the PTE in soil [7].
assessment is an important research tool to evaluate the level Furthermore, the United States Environmental Protection
of population exposure to contaminant sources that can be Agency developed the Integrated Exposure Uptake Bioki-
dangerous for its health and quality of life. This research is netic Model (IEUBK) to evaluate the risk of Pb exposure [8].
significant due to the fact that tailing damps are multiconta-
IEUBK is a predictive model, which is useful to apply in pla-
minated wastes; moreover Pb is a pollutant that can generate
ces with environmental studies of Pb, and blood studies are
harsh effects in people, especially in children. The lack of
less feasible to develop. The IEUBK use values and equa-
urban planning and awareness encouraged that settlements
with new families were developed next to tailing damps with- tions that represent Pb exposition, absorption and biokinetics
out concern about the inhabitant’s exposure to Pb and other in children’s population. Rates of children’s intake of dust,
metals. This manuscript proposes the use of models like the water, air and food, are considered, based on environmental
IEUBK, as a tool for risk assessment and studies related with information of the site (Pb concentration in soil, dust, water,
urban planning in mining sites. V C 2017 American Institute air, and diet) [9].
of Chemical Engineers Environ Prog, 00: 000–000, 2017 The present study refers specifically to a small town (San
Keywords: lead, risk assessment, mining sites, IEUBK Guillermo), located at the north of Mexico. As a result of
more than fifty years of operation of a beneficiation plant,
that used froth flotation process to concentrates separation.
INTRODUCTION The concentrates were gold (Au), silver (Ag), lead (Pb), cop-
The mining industry has generated the accumulation of a per (Cu), zinc (Zn), and the impurities in the mineral were
great quantity of solid waste for centuries (mining slag and arsenic (As), cadmium (Cd), tin (Sn), and vanadium (V)
tailings). Such wastes proceed from the beneficiation pro- [10,11]. The minerals that were extracted and processed from
cess; its composition varies according to the conditions of the plant were specially: argentiferous, argentiferous lead,
each process, causing polluted sites. The main potentially and argentiferous lead-copper, these had gold ore and sul-
toxic elements (PTE) that are present in mining wastes are: phurous forms [galena (PbS), sphalerite (ZnS), greenockite
Lead (Pb), Cadmium (Cd), Zinc (Zn), Arsenic (As), Selenium (CdS), carbonates and oxides] [11].
(Se), Mercury (Hg) [1,2]; being Pb and Cd the pollutants that The objective of this research was to know the Pb con-
are frequently found in mining zones of Mexico [3]. centration and dispersion in a habited area, and to esti-
mate the risk for children population in the site through
C 2017 American Institute of Chemical Engineers
V IEUBK.

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2017 1
Figure 1. Geographical location of inactive beneficiation plants in the state of Chihuahua. [Color figure can be viewed at
wileyonlinelibrary.com]

in the research area is cold and semidesert (BSk), with a


maximum average temperature of 1048F and a minimum
temperature of 6.88F, medium precipitation of 350 mm per
year, and an average of 60 days of rainfall.

Sampling
The sampling was in the inhabited area adjacent to the
tailing dams, it was systematic in a radial grid (spiral) with
100 m circles of arrangement and angles of 158 according to
Mexican regulation NMX-AA-132-SCFI-2006 (Figure 3) [12].
The samples location was done through a GPS, Thales model
2004. 52 samples of surface dust from sidewalks, recreation
areas, corners, and street edges were collected according to
the procedures of the Environmental Protection Agency of
the United States AP-42 appendix C.1 y C.2 [13].

Mineral Composition
Figure 2. Aerial view of residential area adjacent to mining In order to identify the mineral composition of the
waste. [Color figure can be viewed at wileyonlinelibrary. wastes, the following analyses where done in an integrated
com] sample of 75 mm of particle size: X-ray diffraction (XRD) by
SIEMENS equipment modelD5000, Energy dispersive spec-
troscopy (EDS) with scanning electron microscope JEOL
METHODOLOGY JSM-5800 LV tungsten filament and EDX2AF software, and
quantitative analysis by optical plasma spectrometry (ICP-
Location and Features of the Site OES) Thermo Jarrell Ash IRIS/APDIV equipment.
The area of analysis was located in San Guillermo,
Aquiles Serdan, in Chihuahua State, at an elevation of 1,512 Dust Characterization
masl (Figure 1). An analytical evaluation of pH, CE (electric conductivity),
The mining waste deposits (tailing dams) were located at CEC (cation exchange capacity), and OM (organic matter)
400 m away from a residential area. These are deposits of a was don from dust samples made with a particle size of
thin material of an approximate total volume of 7,500,000 m3 75 mm [13]. pH and CE measurements were done accord-
(Figure 2). According to K€oppen0 s classification, the weather ing to Mexican regulation [14]. The CEC was determined

2 Month 2017 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 3. Residential area and sampling points. [Color figure can be viewed at wileyonlinelibrary.com]

Table 1. Parameters used in USA and Latin America. Statistical Analysis


In order to estimate the risk in the residential area and
USEPA, Latin adjacent site, first a normativity analysis was done, through
Parameters 1994 America the Anderson-Darling test, with concentration data of dust.
Time (h) passing outside a 4 6 The statistical analysis was done with software Minitab 16.
child 3–7 years Median values, minimum (25%) and maximum (75%) quar-
Diet (mg Pb/day) 7 9.3 tiles of the data were determinate.
Daily water intake (L/day) 0.59 max. 1
child 6–7 years Risk Analysis IEUBK Model
Daily intake of soil 350 Data of the pollution source in the site were considered.
(mg/day) unpaved street The concentrations of total Pb in dust of the residential area,
Daily intake of soil 85–135 200 were pondered into model. The parameters considered for
(mg/day) paved street the risk analysis as Pb intake and inhalation, were supported
Factor weight soil/dust (%) 45 66 by Diaz Barriga et al., for places located near mining sites in
Air concentration 0.15 [6] 1.92 Latin America [9] and by the Environmental Protection
(mg Pb/m3) Agency for places in United States [8]. In Table 1, are shown
Concentration in water Site – 2.3 the parameters applied into the IEUBK model.
(average) (mg Pb/L) Three scenarios were set up in order to the Pb concentra-
Pb concentration in the site Actual values tion in dust. Scenario A was for minimum value, scenario B
(mg kg21) for median value and scenario C for maximum value.

RESULTS AND DISCUSSION

according to 9081-EPA method [15]. Total determination of Mineral Composition


C and inorganic C was done in a LECO CS-244 analyzer The mineral composition of the integrated sample, deter-
with infrared detection in concordance to method 415.1 mined by DRX is present in Figure 4, the waste was consti-
[16]. The OM was calculated from organic C using the fac- tuted by sulfur (S6), quartz (SiO2), sphalerite (ZnS), selenite
tor 1.724 of Van Bemmelen [17]. Total organic carbon (CaSO4-2H2O), hematite (Fe2O3), jarosite (K(Fe3(SO4)2
(TOC) was obtained by means of the difference between (OH)6)), and goethite (Fe31O(OH)).
inorganic and total C. The main element composition obtained by EDS from the
mining waste sample was (Figure 5): Fe (53.42%), S
Total Metal Quantification (19.81%), O (16.17%), Ca (6.57%), Si (3.33%), and Al (0.70%).
Total metal determination of Pb, Fe, As, and Cd was done The elements in the mining waste sample set up through
for dust, according to the general procedure of Mexican reg- a quantitative chemical analysis with ICP-OES are present in
ulation [7]. Samples were digested according to EPA method Table 2.
3051 [18]. An uncontaminated soil-sample was considered for Quantitative and EDS analyses (Figure 5; Table 2) con-
the analysis, triplicate samples were taken and analyzed by firmed the Pb presence in the mining waste. This pollutant
atomic absorption (AAS) with hydride generator GBC brand can be dispersing by the wind, water overflow, solubilizing
AVANTA SIGMA. and its mobilization capacity [1]. The mineralogy by DRX
In order to obtain the isoconcentration and dispersion of demonstrated the presence of sulfur (S6), sphalerite (ZnS),
Pb in the researched area, data of total concentration of Pb hematite (Fe2O3), jarosite (K (Fe3 (SO4)2(OH) 6)), and goe-
were evaluated using the software ArcGIS 10.1. thite (Fe31O (OH)). This indicates that the present Pb may

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2017 3
Figure 4. Mineralogical composition of mining waste. [Color figure can be viewed at wileyonlinelibrary.com]

Table 2. Analysis of the mining waste by ICP-OES.

Element mg kg21
As 1183 6 195.2
Ba 48.9 6 8.9
Ca 28232.1 6 1322
Cd 44.5 6 2.4
Cr 3.8 6 0.7
Cu 63.1 6 2.9
Fe 115127.6 6 6173.2
K 2029.7 6 5.79
Mg 837 6 58
Mn 894.3 6 36.8
Na 242.8 6 15.5
P 192.1 6 35.8
Pb 3449.1 6 165
S 26662 6 3488
Si 16.5 6 2
Figure 5. EDS analysis and image mining waste sample dif- Sr 28 6 1.4
fraction. [Color figure can be viewed at wileyonlinelibrary. Ti 63 6 7.4
com] V 15.1 6 1.7
Zn 1984.9 6 53.2
Zr 12.2 6 0.5
be reacting with them to form leachable or stable complexes,
according to the physicochemical characterization of the dust
samples as sulfates (Pb(SO4)2), oxyhydroxides (Pb2O3),
correlation between pH and fractions silt/clay, indicating the
(Pb(OH)2) y carbonates (PbCO3) This pollutant can be dis-
ability to hold and exchange with metal minerals (Fe, S) and
persing by the wind, water overflow, solubilizing, and its
thus the possible formation of compounds such as sulfates,
mobilization capacity [19,20].
carbonates and oxyhydroxides shaped-scabs or efflorescence
[19].
Dust Characterization According to the CE values in dust, it was classified as
The physicochemical parameters of the unpolluted sam- nonsaline [14]. The CEC (5.3 C mol(1)kg21 – 19.8 Cmol (1)
ple and dust of the inhabited area are present in Table 3. kg21) and the contents of OMw/w (0.3–1.7%) in the dust are
The dust classification, according to its pH was from moder- considered low, less than the reference unpolluted soils
ately alkaline to strongly alkaline (pH  7.7). If the pH is (32.3 Cmol(1)kg21 and 4.7%). This indicates that the soil
alkaline, Pb is adsorbed by the soil colloids, which explains has been deteriorating throughout time, caused possibly by
the high contents of Pb in dust (Table 3) [21]. There is a the dispersion of the mining wastes. Also, it indicates that

4 Month 2017 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
the predominant clays are kaolinite (almost zero CEC) and in dust. 78.8% of the samples exceed the Rc. Pb concentra-
mica (low CEC) as well as low fertility [14]. tion on samples was between 88.4 6 2.6 and 7,242 6 100.4 mg
The analyses specify that the kind of dust according to kg21 (18 times above Rc) this registered at 400 m away from
the unified system of soil classification is silty clay loam [22]. the wastes in the 25 point (Figure 6). At 800 m of mining
Therefore, it tends to have a low water retention and high wastes, the concentrations decrease to 2397 mg kg21 (6
permeability; they are very easily eroded due to climatic times above Rc).
phenomena (wind and water). Due to its composition, the Total Pb concentrations in dust collected from sidewalks,
dust tends to adsorb and transport heavy metals that were corners and boundaries of paved streets in the residential
kept in the clay surface [23,24]. area adjacent to the mining wastes, confirm the existence of
the dispersion and mobility of Pb present in the mining resi-
dues, transported mainly by the wind. The direction of the
Dispersion of Total Pb dominants winds comes from the South and the East (from
In Figure 6, the dispersion of total Pb in the study area is tailing dams to the residential area) [25].
presented. Pb concentrations on dust samples corresponding Polluted material is transported from the air by the rain,
to the residential area were compared with the reference and falls to the soil or superficial water. Furthermore, by
concentration (Rc) for residential soil (400 mg kg21) denoted the surface runoff in the tailing dams that have a down-
in the Ref. 7, this because in Mexico there is not a Rc for Pb ward inclination of 17.5% towards the residential area.

Table 3. Physicochemical parameters of the samples. Table 4. Pb concentrations obtained in dust.

Physicochemical Unpolluted Dust (mg kg21)


parameters soil inhabited area Statistical range (95% confidence)
pH 1:2 6.1 7.7–10.8 Minimum Maximum
CE1:5 (dS/m) 42.7 0.27–1.06 Area N (Q1) Median (Q2)
CIC (Cmol(1)kg21) 32.3 5.3–19.8 Inhabited 52 375 709 1363
MO (%w/w) 4.7 1.0–1.7 (Dust)

Figure 6. Dispersion of total Pb in the study area. [Color figure can be viewed at wileyonlinelibrary.com]

Table 5. Pb concentrations in blood and the probability percentage >10 mg dL21.

Parameters
Latin American United States
Pb in Probability Pb in Probability
Pb in dust blood % blood %
(mg kg21) (mg dL21) 10 mg dL21 (mg dL21) 10 mg dL21
Scenario 375 8.00 31.68 4.18 3.19
A
Scenario 709 12.15 66.08 6.83 20.82
B
Scenario 1363 18.57 90.61 11.18 59.42
C

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2017 5
Released Pb in the environment is kept in the soil, it is This model estimated the Pb level in childrens blood from
commonly found as oxides, hydroxides, and complex oxya- ages of 0 to 7 years old. Levels higher than 10 mg dL21, can
nionic metals [1]. cause health problems in people NOM-199-SSA1–2000 [28].
Pb is one of the main pollution problems in Latin America The results of estimated Pb-concentrations in blood (mg
[26], such type of pollution affects marginalized areas. Some Pb dL21) are presented in Table 5, also the probability per-
of the factors, such as sparse vegetation cover in child recre- centage of concentrations higher than 10 mg dL21. This about
ation areas, allow that the route floor/dust be one of the two runs (parameters of Latin America and United States) in
main exposure source [27]. the three scenarios.
The Pb dispersion proved that the effect of the wind and In the Scenario A with the minimum concentration of Pb
hydraulic events contribute to diffuse the metal through the in dust (375 mg kg21), the risk probability of having Pb in
inhabited area, being higher concentration at the middle of blood stream above 10 mg dL21 was 31.68% considering
the place, and decreasing towards either side. parameters for Latin America (LA), with paved streets. In the
same scenario A, but considering the living conditions in
United States (USA), the risk probability was 3.19%. With a
Risk Analysis IEBUK Model median concentration of Pb in dust (709 mg kg21) in sce-
Concentrations of Pb in dust obtained in the statistical nario B, the probability increased up to 66.08% for LA and
analysis are present in Table 4. There were considered three 20.82% for USA. Under maximum critical conditions of Pb
scenarios with such values (A 5 minimum, B 5 median, concentration in dust (1,396 mg kg21), the probability of
C 5 maximum) to evaluate risk analysis in the research area. having Pb concentration in blood above 10 mg dL21 was
90.61% in LA and 59.42% in USA (Table 5).
The probability of Pb in blood above 10 mg dL21 is higher
for LA places than in USA in the three scenarios, also this
probability increases with the rise of Pb in dust. However, in
scenario C the probability for both cases (LA and USA) is
considerably high.

Pb in Dust and Blood Association


Pb concentrations in dust <100 mg kg21 predicted that Pb
concentration in children’s blood will be by the order of 3.86
mg dL21 according to the parameters from LA, and 1.74 mg
dL21 according to parameters for USA. Responses obtained
with the model in every scenario with both parameters indicate
a curvilinear relationship between Pb levels in children’s blood
and Pb concentration in dust (Figure 7). This data matches
with Mielke et al. and Mielke et al. in Luisiana, New Orleans,
Syracuse, and New York, from the United States. Also matches
with Valles-Aragon et al. in a research made in an ex-foundry
close to the place of this research. They obtained the same
Figure 7. Curve of the relationship between soil Pb concen- behavior considering IEBUK parameters [29–31]. Furthermore,
trations and blood Pb concentrations. [Color figure can be Romieu et al. determined that IEUBK for Pb-contaminated sites
viewed at wileyonlinelibrary.com] in LA have a high potential to predict Pb in children’s blood if
the real data of the site are used [26].

Table 6. Toxicity and Health effects in children from exposure to Pb in soil and dust.

Pb concentration
Pb concentration in dust in blood Health effects in children References
The first few mg of Pb Multiple studies have shown [34–36]
the strongest effects on the
intelligence quotient (IQ)
8 a 500 mg kg21 1 a 10 mg/dL The IQ decreased 7.4 point [35]
<172 mg kg21 <5 mg/dL The IQ decreased 4.9 point. [37]
172–500 mg kg21 5–9.9 mg/dL IQ (91.3 vs. 86.4)
172–500 mg kg21 5–10 mg/dL The IQ decreased 5.0 points [38]
compared with children with
levels of 1.2 mg/dL
500 mg kg21 <10 mg/dL (ADDH) Attention Deficit Dis- [6,33,39–44]
order and Hyperactivity
–Half a reduction in testing:
Reading 5 0.51
Writing 5 0.49
Mathematics
–Kidney damage
–Dental caries
–Delay at puberty;
Men
Women

6 Month 2017 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Health Effects of Pb 7. NOM-147 (2004). Norma Oficial Mexicana NOM-147-SEM-
Toxicity caused by Pb and its effects on children’s health, ARNAT/SSA1–2004 Que establece criterios para determi-
displays that they are more vulnerable. Children generally nar las concentraciones de remediaci on de suelos
eat polluted dirt and dust because of their compulsive contaminados por arsenico, bario, berilio, cadmio, cromo
behavior of taking their hands into their mouths. Children hexavalente, mercurio, nıquel, plata, plomo, selenio, talio
inhale dust that is contaminated with Pb more easily due to y/. Secretarıa de Medio Ambiente y Recursos Naturales,
their physiology [6]. Mexico.
The exposure of children to inorganic Pb has been mainly 8. USEPA (1994). Reference manual: Documentation of
associated to problems of neurological nature, impairment of updates for the integrated exposure uptake biokinetic
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area in San Guillermo, Aquiles Serdan. The lack of environ- Recursos Naturales, Mexico.
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