Origin of salinity and hydrogeochemical features of porous aquifers from northeastern Guanabara Bay, Rio de Janeiro, SE - Brazil

Journal of Hydrology: Regional Studies 22 (2019) 100601

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Origin of salinity and hydrogeochemical features of porous aquifers from northeastern Guanabara Bay, Rio de Janeiro, SE - Brazil

T

Olga V.O. Gomesa,b, Eduardo D. Marquesc, Vinicius T. Küttera, José R. Airesd, ⁎ Yves Travie, Emmanoel V. Silva-Filhoa, a Programa de Pós Graduação em Geociências (Geoquímica), Universidade Federal Fluminense, Outeiro São João Batista s/n – Centro, Niterói, RJ, 24020-141, Brazil b Instituto Três Rios, Universidade Federal Rural do Rio de Janeiro, Três Rios, RJ, 25802-210, Brazil c Geological Survey of Brazil, Belo Horizonte Regional Office, Belo Horizonte, 30140-002, Brazil d Abast, PETROBRAS, Rio de Janeiro, RJ, Brazil e Laboratoire d’Hydrogéologie, Faculté de Sciences, Université d’Avignon, 84000, Avignon, France

A R T IC LE I N F O

ABS TRA CT

Keywords: Chloride/bromide ratio PHREEQC hydrochemical modeling Guanabara Bay porous aquifer Regional hydrogeochemistry Tertiary/quaternary sediments

Study Region: Porous aquifer system of Northeastern Guanabara Bay, Rio de Janeiro, Brazil. Study Focus: The present work aimed to comprehend the geochemical processes responsible for the considerable range of salinity (48 to 5651 μS. cm−1) through chemical composition of groundwater (hydrogeochemical modeling through PHREEQC) allied to chemical ratios (Cl/Br ratio) and stable isotopes data (δ18O and δ2H). New hydrological insights for the region: The PHREEQC modeling showed that high pH and low pe values conditioning the main processes controlling the hydrogeochemical evolution of groundwater in that region. The salinity origins should be explained by 4 hypotheses: 1) a group related to recharge zones, close to the basin headboard or connected to the fractured aquifers from the basement rocks (low Cl/Br ratio and predominance of light δ18O and δ2H isotopes; 2) a group formed by groundwater with high Cl/Br ratio and predominance of heavy δ18O and δ2H isotopes, associated to dissolution processes of Tertiary brackish water environment sediments; 3) a group formed by groundwater with low Cl/Br ratio, high Cl− concentrations and low δ18O and δ2H, related to groundwater under influence of Caceribu River (high content of domestic effluents); and 4) a group composed by groundwater with high salinity, high Cl− concentrations and enrichment of δ18O and δ2H, located at a mangrove area, where the influence of seawater intrusion in the aquifer is recognized.

1. Introduction The Guanabara Bay Hydrographic Basin (mainly composed by the hydrographic basins of Macacu and Caceribu Rivers) has an important role for the population of several part of Rio de Janeiro Metropolitan Region (RJMR) as it represents one of the main water supply. At northeastern part of this hydrographic basin is located the Itaboraí municipality, which is undergoing intense urbanization process, as consequence of the installation of the Petrochemical Complex of Rio de Janeiro (COMPERJ), started in 2008. At this region, it is found an important geological unit of Rio de Janeiro State, the Macacu Sedimentary Basin, which is also an important coastal aquifer system (Macacu Coastal Aquifer). The Macacu Coastal Aquifer is composed by Tertiary clastic sediments, which can ⁎

Corresponding author. E-mail address: emmanoelvieirasilvafi[email protected]ff.br (E.V. Silva-Filho).

https://doi.org/10.1016/j.ejrh.2019.100601 Received 13 September 2018; Received in revised form 1 March 2019; Accepted 4 March 2019 Available online 12 March 2019 2214-5818/ © 2019 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).

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Fig. 1. Location of the aquifers sampled and monitoring wells in the Macacu sedimentary basin by Ferrari (2001) adapted.

reach depths over than 200 m, and Quaternary sediments from riverine-lacustrine and fluvial-marine environments, reaching depths about 40 m (Fig. 1). Thus, the installation of the Petrochemical Complex became an important issue for the government authorities due to the possible environmental impacts on that region. For this reason, some environmental studies are in progress, mainly focused on the preservation of the water resources. Generally, coastal areas constitute vulnerable ecosystems subject to severe anthropogenic pressure and natural hazards such as sea-level rise, land subsidence, coastal erosion and flooding and salinization of groundwater. The intrusion of saltwater into coastal aquifers is a widespread phenomenon that gradually causes the problem of groundwater salinization (Trabelsi et al., 2007; Gattacceca et al., 2009; Ghiglieri et al., 2012; Giambastiani et al., 2013). The monitoring of electrical conductivity (EC) from groundwater in Itaboraí reveals great heterogeneity in concentrations of dissolved constituents, which suggests salinization processes by seawater encroachment in Macacu Coastal Aquifer (Gomes et al., 2013). Salinization of coastal aquifers is explained generally in terms of lateral seawater intrusion into the aquifer, but other processes may be involved, such as flow of saline groundwater from adjacent or underlying aquifers, anthropogenic contamination due to agriculture or infiltration of sewage effluents (Gassama et al., 2012; Farber et al., 2007; Kass et al., 2005). Whatever the salt source, its recognition is very often masked by the activation of water–rock interactions directly related to increase in water ionic strength, whose effects overlap those ones caused by the salt source (de Montety et al., 2008; Fidelibus and Tulipano, 1990; Ghiglieri et al., 2009; Giménez and Morell, 1997; Howard and Lloyd, 1983; Yamanaka and Kumagai, 2006). Furthermore, there are cases where salinization is due to the presence of connate fossil waters (Worden et al., 2006). Saltwater encroachment in groundwater generally is assessed by some ions ratios, namely Mg/Ca, K/Na, Na/Ca, Cl/HCO3 and Na/Cl ratios and mainly Cl/Br ratio (Zilberbrand et al., 2001; Vengosh et al., 2002; Vengosh and Rosenthal, 1994; Vengosh and BenZvi, 1994; Vengosh and Pankratov, 1988; Hem, 1985). These ions ratios are worldwide used because they give important information about dissolution of geological material and other geochemical processes, which will influence in the water chemical composition. The Cl/Br ratio is an important tool for monitoring the salinization of groundwater due the conservative behavior of these ions (Alcalá and Custodio, 2008; Lorenzen et al., 2012; Ortega et al., 2015), and its associations with Cl− concentrations could inform the origin of the groundwater salinity, in other words, whether the salinity is coming from the marine aerosol or could be influenced by aquifer materials, atmospheric precipitation increased by evaporation and anthropic sources (Custodio and Llamas, 1983). According to Davis et al. (1998), the abundancy of Cl− and Br− in the environment presents a primordial difference, both in water and rock. Cl− is about 40 to 8000 times abundant than Br−. A little change in the dissolved Br− amount trigger a significant difference in the Cl/Br ratio. The same author studied the Cl/Br ratio in shallow aquifers from Alberta, Kansas and Arizona (USA) which ranged from 100 to 200. Freshwater influenced by domestic sewage the range was between 300 and 600; in aquifers from urban areas, influenced by streets runoff, this ratio ranged from 10 to 100; and for groundwater associated to geological unities containing halite, the Cl/Br ratio ranged between 1000 and 10,000; for the rainwater in those locations ranged from 50 to 150. Davis et al. (1998), 2001) also demonstrated that coastal aquifers from USA presented Cl/Br ratio of about 400 and the groundwater from the interior presented values < 150. In Southeastern Australia, systematic measurement of Cl/Br ratio in rainwater displayed values between 180 and 220; for coastal aquifers influenced by seawater intrusion, the ratio values oscillated between 400 and 1300 (Cartwright et al., 2006). For Davis et al. 2

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(1998), (2001) the Cl/Br ratio from seawater is about 650. Alcalá and Custodio (2008) highlighted that aquifers from Portugal and Spain are directly influenced by seawater encroachment and also have Cl/Br ratio of 655, while in the interior of these countries this ratio ranged from 200 to 500; halite-rich aquifers in these countries presented Cl/Br ratio between 5000 and 6000. Still in this study, the authors showed that agricultural areas affected by pesticides presented this ratio values about 300. Additionally, the Cl/Br ratio has become an effective tool in studies of surface water and groundwater with low-to-moderate salinity (Ortega et al., 2015). Even Cl− and Br− being conservative ions, the sorption of Br− has been reported in some studies (Tennyson and Sttergren, 1980; Leap, 1982; Bowman, 1984; Davis et al., 1985; Bowman and Rice, 1985), however, generally only 10% of dissolved Br− is adsorbed by clay-minerals, soil and organic matter; in acid solutions (pH ˜ 4.7), the sorption can reach about 15–20% (Boggs and Adams, 1992). Considering the salinity in groundwater is due to the precipitation/dissolution process, the use of hydrogeochemical modeling could be a valuable tool to describe the spatial and temporal variability of groundwater composition (Alley, 1993; Silva-Filho et al., 2009). The stable O and H isotopes (δ18O and δ2H) together with the Cl/Br ratio, could help to understand the interactions among groundwater, surface and meteoric water, besides to determinate groundwater recharge and discharge areas and also reveal evaporation process or mixing with seawater (Cary et al., 2015). Thus, the aim of this study is to characterize the groundwater chemistry from Macacu Coastal Aquifer and understand main processes affecting the hydrogeochemical evolution of groundwater in the Guanabara Bay Region. 2. Study area The study area is located at Itaboraí municipality, northeastern Guanabara Bay, between the Guapi-Macacu and Caceribu rivers (Fig. 1). According to SEMADS (1999), the region weather is classified as subtropical to tropical and the annual temperature average is about 21 °C. The greatest temperatures occur between December and March, but February is the warmest month, presenting temperature average of about 25 °C. July is the coldest month and shows temperature average of about 20 °C. Historic data of rainfall (time series of 31 years) point out annual average about 1800 mm, presenting the wet season between November and January and the dry season between June to August, sometimes anticipating to May and extends to September (DRM, 1981). According to SEMADS (1999), the annual average evaporation, in the most part of the study region, is about 900 mm. Located at the geological domain of Guanabara Graben, which is inserted in the Ribeira Fold Belt, the study area belongs to a Neoproterozoic geotectonic domain (CPRM, 2001). According Almeida (1977, 1981), the Ribeira Fold Belt integrates the geotectonic framework at Southeastern Brazil, surrounding the São Francisco Craton, together to others orogeny as Brasília Fold Belt (westward) and Araçuaí Fold Belt (eastward), which took place during Brazilian/Pan-African Orogenesis. The structuration of Guanabara Graben is dated from the Paleocene, building up the Macacu sedimentary basin at Eocene during the graben evolving under strong NW-SE extensional system (Ferrari, 2001). In Eocene, the Paleocene sediments from Macacu basin were reworked, contributing to the formation of Itambi conglomerate, which marks the transition between Tertiary and Quaternary, together with the intense erosion in the northern border of Macacu basin, showing a marked gap between Serra do Mar Mountains and the basin (Ecologus-Agrar, 2005). An interesting hydrothermal event in the study area, at Tanguá municipality, was related to the alkaline magmatism dated from Neocretaceous to Eotertiary, which are found in some regions of Rio de Janeiro State. The Tanguá Alkaline Complex is responsible to the lode fluoride mineralization in structures toward NE-ENE (Sant’anna and Riccomini, 2001; Coelho, 1987; Sonoki and Garda, 1988). 2.1. Hydrostratigraphic units The study area is composed by four hydrostratigraphic units, namely: the Macacu Aquifer (Tertiary sediments), the AlluvialLacustrine Aquifer and the Fluvial-Marine Aquifer, both sediments of Quaternary, and the Fractured Aquifer from the crystalline basement (Fig. 2). According to Schlumberger (2007), the Alluvial-Lacustrine Aquifer is an unconfined aquifer composed by sandy and clayey sediments (with large variety of mineralogical composition) and organic matter, thickness about 20 m and an extraction discharge from 10 to 20 m3 h−1. The Macacu Aquifer comprises sand and conglomerates from the Macacu Formation, intercalated to pelitic lacustrine facies, constituting in a multilayer semi-confined aquifer. The extraction discharge from this aquifer has a range from 5 to 42 m3 h−1, with discharge of about 0.9 m3 h−1 m−1. The Fluvial-Marine Aquifer is represented by the flooded terrains in the mangrove area from Guapimirim Environmental Protection Area (EPA), composed by clay sediments, organic matter enriched, located in the coastal region and in the end-member of the river canals toward sea. Studies suggest an average extraction discharge from 5 to 10 m3 h−1 (Ecologus-Agrar, 2005). The main groundwater outflow system of the studied aquifers is through the porous matrix toward Guanabara Bay, which is in concordance with the surficial streams, the regional groundwater outflow is given from east to west (Fig. 2). Locally, those alluvionar aquifers contribute to the maintenance of rivers base level, due to the porous hydraulic connection among them (Schlumberger, 2007). 3. Material and methods Six sampling campaigns were carried out monthly between August 2009 and January 2010 (n = 56). Four multilevel wells were monitored (P-01, P-02, P-03 and P-04, Fig. 1), each one with screens installed in two or three different depths according to the 3

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Fig. 2. Structural framework Basin Macacu (Meis and Amador, 1977; Penha et al., 1979; D’Alcolmo et al., 1982) and lithostratigraphic subunits of Macacu Formation by Ferrari (2001) adapted.

4

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Fig. 3. Log of well P-01 showing groundwater extraction at various levels (Schlumberger, 2008).

different aquifer layers, as exemplified in the well log in Fig. 3. The P-05, installed in the mangrove area, has only one groundwater monitoring level, located at 15 m depth. The Table 1 presents a summary of the features from the monitored wells, with more than one groundwater monitoring level in different depths, ranging from 17 to 148 m. Therefore, the hydrostratigraphic units sampled were the Macacu Aquifer (Tertiary), the Fluvial-Marine Aquifer and the Alluvial-Lacustrine Aquifer (Quaternary). For this work, the Macacu Aquifer, due to its thickness, was divided in three other sub-aquifer units, namely shallow, medium and deep Macacu. In the field work, before to collect the sample, it was performed measurements of the water level and the volumes contained in each well in order to perform the purge. The water samples were collected using a submersible pump (model WSP-12V-4-WaTerra) coupled to a polyethylene hose. All samples were filtered with 0.45 μm cellulose acetate membrane and preserved in thermal boxes on temperature about 4 °C. The parameters: Electrical conductivity (EC), total dissolved solids (TDS), temperature, pH and Eh were performed in situ by a Hanna Instruments® multi-parameter probe. In laboratory, the major ions (Na+, K+, Ca2+, Mg2+, Cl−, SO42- and Br−) were carried out without previous dilution by ion chromatography with the equipment Metrohm® (model 861) with an automatic sampler (model 863). The HCO3 concentrations were obtained by using methods of volumetric dosage. The ion balance error calculated for all samples showed values under ± 10%, accepted error limit for the electrical conductivity range, according Custódio and Llamas (1983). The hydrogeochemical modelling was carried out by PHREEQC (Parkhurst and Appelo, 1999), which calculated mineral equilibrium and dissolved ion speciation. The stable isotopes analysis (δ2H and δ18O) was performed for 59 samples, including 56 from groundwater and 3 from rainwater, in the Hydrogeology Laboratory from Université D’Avignon, France, by mass spectrometer (Finnigan Delta S). All values are referred to the SMOW standards (Craig, 1961) and the analytical deviation reproducibility of ± 0.1‰ for δ18O and ± 1‰ for δD. Aiming to identify the marine influence on the study area, daily measurements of water table level and EC were performed by pressure transducers (divers) from October 2009 and January 2010 in the wells P-01C and P-05, which are shallower and closer the

Table 1 Characteristics of wells sampled (SCHLUMBERGER, 2008 – adapted). Well

Level

Thickness filter (m)

Lithology

Hydrostratigraphic unit

P-01

A B C A B C A B A B –

126 - 132 63 - 65 18 -20 145.9 - 147.9 123.5 - 124.5 24 - 26 114.8 - 120.8 14.8 - 16.8 89.4 - 93.4 25.4 - 29.4 11.5 – 15.5

Sandy clay / loamy sand with interspersed with sandy levels greenish gray. Sandy clay interspersed with levels predominantly sandy, greenish gray (mudstone). Sandy with granulometry coarse to fine, clayey, gray. Sand with medium to coarse grain size, silty-clay, gray. Sandy with granulometry fine to coarse, gray. Sandy with fine to medium grain, gray. Sandy with granulometry fine to coarse, gray. Sandy with granulometry fine to coarse, low clay, light gray. Boulders of quartz and feldspar with fragments of argillite. Sandy clay, gray. Sandy with granulometry fine to coarse, gray.

Macacu Aquifer Macacu Aquifer Alluvial-Lacustrine aquifer Macacu Aquifer Macacu Aquifer Macacu Aquifer Macacu Aquifer Alluvial-Lacustrine aquifer Macacu Aquifer Alluvial-Lacustrine aquifer Fluvial-Marine Aquifer

P-02

P-03 P-04 P-05

5

Aquifer Systems

Deep Macacu Medium Macacu Alluvial-Lac. Deep Macacu Deep Macacu Shallow Macacu Deep Macacu Alluvial-Lac. Medium Macacu Alluvial-Lac. Fluv-mar Deep Macacu Medium Macacu Alluvial-Lac. Deep Macacu Deep Macacu o Shallow Macacu Deep Macacu Alluvial-Lac. Medium Macacu Alluvial-Lac. Fluv-mar Deep Macacu Medium Macacu Alluvial-Lac. Deep Macacu Deep Macacu Shallow Macacu Deep Macacu Alluvial-Lac. Fluv-mar Deep Macacu Medium Macacu Alluvial-Lac. Deep Macacu Deep Macacu Shallow Macacu Deep Macacu Alluvial-Lac. Fluv-mar – Deep Macacu Medium Macacu Alluvial-Lac. Deep Macacu Deep Macacu Shallow Macacu

ID

P-01 A (08/09) P-01B (08/09) P-01C (08/09) P-02 A (08/09) P-02B (08/09) P-02C (08/09) P-03 A (08/09) P-03B (08/09) P-04 A (08/09) P-04B (08/09) P-05 (08/09) P-01 A (09/09) P-01B (09/09) P-01C (09/09) P-02 A (09/09) P-02B (09/09) P-02C (09/09) P-03 A (09/09) P-03B (09/09) P-04 A (09/09) P-04B (09/09) P-05 (09/09) P-01 A (10/09) P-01B (10/09) P-01C (10/09) P-02 A (10/09) P-02B (10/09) P-02C (10/09) P-03 A (10/09) P-03B (10/09) P-05 (10/09) P-01 A (11/09) P-01B (11/09) P-01C (11/09) P-02 A (11/09) P-02B (11/09) P-02C (11/09) P-03 A (11/09) P-03B (11/09) P-05 (11/09) Rainfall (11/09) P-01 A (12/09) P-01B (12/09) P-01C (12/09) P-02 A (12/09) P-02B (12/09) P-02C (12/09)

3.7 – 626 5.7 6.8 3.8 – 7.8 122 158 – – 17 745 10.4 – 10.0 9.8 9.8 141 178 1246 2.1 2.0 459 4.3 3.9 5.0 5.6 6.9 919 3.2 2.7 444 14.2 10.8 4.4 4.0 9.1 803 – 2.8 2.4 573 18.2 6.1 6.2

Cl− (mg/L) 0.78 20 – 4.0 0.03 0.01 – 5.20 22.53 14.55 – – 29.70 15.05 6.77 9.44 7.96 5.64 0.04 28.44 19.77 387.76 0.77 0.15 4.00 7.78 5.75 18.88 9.55 4.24 120.1 1.39 1.67 0.56 4.71 3.96 7.87 5.25 5.14 100.7 – 1.35 1.70 0.98 18.19 7.35 10.28

SO4−2

229 157 176 182 30 80 328 240 50 68 – 171 50 47.4 150 35.1 25 183 127 330 50 150 318 105 37 204 30.1 52 270 224 100 156 90 34 142 20.2 64.0 212 184 761 – 225 101 38 208 102 48

HCO3−

0.02 0.02 – 0.04 0.05 0.06 0.04 0.05 0.23 0.33 6.02 0.02 – – 0.07 0.06 – 0.04 0.04 0.22 0.40 5.86 0.03 0.03 6.56 0.05 0.04 0.06 0.05 0.05 3.99 0.03 0.02 2.27 0.08 0.05 0.05 0.04 0.06 6.61 – 0.02 0.02 3.12 0.11 0.06 0.06

Br−

76.4 48.4 143.7 9.1 4.2 18.4 3.2 90.2 33.6 97.1 2.3 107.8 26.3 218 11.8 17.1 5.7 76.5 39.4 164 43.3 725 107.5 34.9 107 27.4 6.0 10.6 107.3 82.1 251.8 56.7 21.8 96.1 29.1 4.9 15.8 56.8 48.6 628.5 – 59.2 24.9 124.4 42.9 6.9 17.5

Na+

Table 2 Hydrogeochemical and isotopic data of aquifers systems of Sedimentary Basin Macacu.

2.4 4.2 18.8 5.9 2.2 5.2 1.6 1.1 8.0 6.4 1.2 6.5 4.9 18.8 7.2 3.5 3.4 1.9 2.5 10.5 16.6 87.1 3.4 4.8 16.7 1.3 2.7 1.7 1.5 5.7 67.0 2.7 2.8 10.6 4.3 1.7 4.1 1.1 3.7 36.3 – 2.7 2.9 11.9 5.3 1.6 4.9

K+

0.9 1.2 19.0 3.7 1.3 2.1 0.8 0.9 6.6 7.8 1.3 0.5 0.7 19.3 2.8 0.9 0.7 0.5 0.6 4.1 4.7 56.5 0.5 0.7 15.0 3.0 0.7 1.5 0.4 0.9 40.9 0.9 0.7 17.9 10.3 0.7 0.01 1.0 9.9 66.7 – 0.3 0.6 22.8 11.4 18.7 0.01

Mg+2

6.4 5.6 181.1 38.1 5.2 7.3 4.9 4.1 16.1 19.4 3.9 12.4 6.2 182.3 39.3 7.3 3.8 5.4 5.3 29.3 23.0 77.3 13.3 8.5 126.3 43.1 7.3 13.5 5.9 9.4 53.0 13.7 7.5 88.9 7.5 7.0 7.8 11.5 16.8 21.3 – 18.7 8.8 116.1 17.8 5.2 4.3

Ca+2

24.94 24.81 24.74 25.78 24.95 26.24 25.24 25.4 25.56 25.6 24.91 25.19 25.11 25.26 26.38 26.02 26.34 26.04 25.81 25.88 26.42 25.36 24.42 24.05 24.86 25.58 25.54 25.58 25.49 24.34 24.46 24.38 24.01 24.88 25.55 25.51 25.57 26.15 24.69 24.47 – 24.39 24.09 24.88 25.55 25.5 25.56

Temp. o C 366 183 2550 376 90 197 375 373 1104 900 – 364 181 2302 343 97 138 375 370 1120 727 5651 349 177 1564 331 75 176 336 340 5526 352 194 1637 362 90 150 381 322 5532 – 354 185 2075 403 76 152

EC (μS/cm) 8.0 6.0 7.0 7.2 6.0 6.7 8.8 8.6 7.7 6.8 – 7.7 6.7 6.2 7.1 6.0 6.1 8.5 7.9 7.3 6.8 6.8 8.0 6.7 6.4 7.2 5.8 6.5 8.4 7.3 6.8 7.6 6.9 6.5 7.0 5.7 6.1 8.3 7.1 6.7 – 7.6 6.6 6.3 7.1 5.7 6.4

pH

1.47 2.07 1.55 4.59 5.29 4.97 0.98 3.05 0.78 1.63 1 0.75 3.05 2.23 4.6 3 5.73 2.06 4.02 0.18 3.11 1.19 0.22 1.09 0.85 1.55 2.6 2.25 −0.22 3.2 0.79 0.55 1.49 1.82 1.61 4.66 4.36 2.64 3.1 0.62 – 0.46 1.63 1.76 1.29 4.9 3.86

pe

379.35 – – 349.52 329.57 137.30 – 387.98 1195.11 1070.76 – – 244.22 – 344.73 – – 244.92 538.65 1420.40 1006.91 479.11 181.15 126.07 157.66 196.27 207.90 194.86 259.69 300.16 519.36 277.23 244.53 441.16 379.40 480.58 213.08 253.07 349.61 273.98 – 294.76 294.36 414.12 358.49 237.24 243.43

Cl/Br (meq/L)

6

−29,48 – – −27,50 – – – – −31.41 – −20,85 −34,14 −36,21 −32,53 – −23,73 −22,77 – −32,53 −20,28 – – −35,36 −36,28 −33,46 −27,36 −25,35 −25,16 −32,97 −32,00 −19,77 −33,80 −35,93 −34,06 −29,47 −25,08 −24,81 −33,84 −30,74 −21,58 −20,76 −34,75 −35,37 −34,15 −33,03 −25,60 −24,29

−3.90 – – −4.73 – – – – −5,19 – −3.92 −5.7 −5.90 −5.18 – −4.16 −3.64 – −5.46 −0,08 – – −5.80 −5.92 −5.45 −4.63 −4.34 −4.34 −5.55 −5.28 −3.91 −5.57 −5.82 −5.48 −4.95 −4.32 −4.27 −5.56 −5.08 −3.93 −1,37 −5.78 −5.85 −5.52 −5.54 −4.42 −4.30

2 8 – 10 – – – – 10 – 11 11 11 9 – 10 6 – 11 −20 – – 11 11 10 10 9 10 11 10 12 11 11 10 10 10 9 11 10 10 −10 11 11 10 11 10 10

d-excess

(continued on next page)

δ2H ‰

δ18O ‰

O.V.O. Gomes, et al.

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Aquifer Systems

Deep Macacu Alluvial-Lac. Fluv-mar – Deep Macacu Medium Macacu Alluvial-Lac. Deep Macacu Deep Macacu Shallow Macacu Fluv-mar –

ID

P-03 A (12/09) P-03B (12/09) P-05 (12/09) Rainfall (12/09) P-01 A (01/10) P-01B (01/10) P-01C (01/10) P-02 A (01/10) P-02B (01/10) P-02C (01/10) P-05 (01/10) Rainfall (01/10)

Table 2 (continued)

4.9 8.5 1139 1.4 2.5 1.8 532 7.5 7.8 5.0 1243 –

Cl− (mg/L) 6.88 5.19 138.7 4.19 0.72 0.56 0.60 1.61 6.52 6.65 148.8 –

SO4−2

188 166 787 – 202 87 29 159 25.3 43 754 –

HCO3−

0.04 0.05 6.53 0.04 0.04 0.03 2.03 0.07 0.07 0.05 4.71 –

Br−

73.1 47.7 864.6 3.9 53.2 24.0 127.9 38.9 7.6 13.3 932.9 –

Na+

1.3 3.8 51.8 0.1 2.7 2.9 12.7 5.0 2.0 4.4 54.1 –

K+

1.0 4.4 51.8 – 0.3 0.4 11.5 8.0 0.7 0.01 31.6 –

Mg+2

8.2 10.8 19.3 0.0 14.5 7.9 55.0 13.1 5.4 3.3 9.8 –

Ca+2

24.45 24.21 24.88 25.53 25.46 25.54 24.5 –

25 25.16 24.48

Temp. o C 350 292 5348 – 352 176 2027 380 71 118 5487 –

EC (μS/cm) 8.3 6.7 6.7 – 7.6 6.8 6.4 7.1 5.7 6.2 6.7 –

pH

0.41 2.46 1.37 – 0.62 1.99 1.77 1.31 5.55 4.12 1.69 –

pe

270.80 365.45 392.99 73.86 128.74 122.03 591.18 261.06 268.50 243.99 595.17 –

Cl/Br (meq/L)

δ2H ‰ −35,08 −31,26 −20,98 −18,62 −35,09 −36,34 −33,07 −34,44 −26,03 −25,24 −20,68 −40,67

δ18O ‰ −5.73 −5.20 −3.95 −2,37 −5.70 −5.86 −5.36 −5.7 −4.39 −4.39 −4.06 −6,40

11 10 11 0 10 11 10 11 9 10 12 11

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Fig. 4. Three-dimensional spatial distribution of EC in sedimentary aquifers Basin Macacu.

coastal line. 4. Results The data from the monitored wells are shown at Table 2. In dry season, the lowest EC value is observed in Deep Macacu Aquifer (71 μS cm−1) and the highest one in Fluvial-Marine Aquifer (5487 μS cm−1). In rainy season the lowest EC value was 48 μS cm−1 (Deep Macacu Aquifer) and 5651 μS cm−1 (Fluvial-Marine Aquifer). The Fig. 4 presents the tridimensional distribution of EC values from the studied aquifers in function of the water level and the distance of the wells from the coastal line. The highest EC values are observed in P-05 (Fluvial-Marine Aquifer), the shallower and closer to coast line, besides the only one installed in the mangrove area (Guapimirim EPA). The lowest EC values are found in P-02B (Macacu Aquifer) located at the border of the basin. Observing the range of EC values, it is noticed there is no great difference between dry and wet season. Regardless of the season and aquifers sampled, it is noticed the wells located up to 14 km from the coast line (P-01, P-04 and P-05) show EC values higher compared to the other ones. This result suggests that those wells are influenced by saltwater intrusion and/or other salinization process. The pH values ranging from 5.7 to 8.8 in dry season, with the highest value for the P-03 A and lowest value in P-02B, both in Deep Macacu Aquifer. The same wells in the rainy season present pH range similar to the dry season (5.7–8.3). As well as EC behavior, the pH range also present large spatial variation, however, an irrelevant seasonal variation. The pe values varied from -0.22 to 5.73, with the highest value in P-02C (Shallow Macacu Aquifer) and lowest at P-03 A, in Deep Macacu Aquifer. However, considering the average pe values from the studied aquifers, the highest is found at Shallow Macacu Aquifer, due to the closeness to the land surface and the lowest ones in Fluvial-Marine Aquifer, obviously due to the mangrove environment. The major ions concentrations versus Cl− concentration (Fig. 5) showed that the Fluvial-Marine Aquifer to have the higher values of Na+, Mg2+, K+, SO42- and HCO3−, while Ca2+ has its higher concentrations in the Alluvial-Lacustrine Aquifer. Magnesium presents the largest range of concentrations on Alluvial-Lacustrine Aquifer varying from 0.57 to 22.84 mg l-1 while the Deep Macacu Aquifer presented concentrations between 0.23 and 18.7 mg l-1. The Cl− concentrations in the Alluvial-Lacustrine Aquifer (shallow aquifer) show a large range (between 9.8 and 158 mg l-1) probably due to the well location relative to the shoreline. The Cl− concentrations show an increase westward (lesser in P-03B and higher at P-04B and P-01C) allowing to infer different hypothesis as i) saline intrusion contamination; ii) aquifers influenced by surface water contaminated by domestic/industrial sewage; iii) natural salt dissolution from older coastal sediments in the aquifer matrix. The major ions concentrations from groundwater represented in Piper-Hill diagrams (Fig. 6), allowed distinguishing three main hydrochemical facies, namely, Ca-HCO3, Na-HCO3 and Na-Cl types. Therefore, based on these hydrochemical features from groundwater, it is possible to notice that 1) in deep aquifer layers, close to the headboard of the basin (dominance of Macacu Aquifer), predominates the hydrochemical facies Ca-HCO3 (P-02) and Na-HCO3 (P-03); 2) in deep and intermediate aquifers at central part of the basin, dominates, respectively, the Na-HCO3 type (P-01 A and P-01B) and Na-Cl type (P-01C); 3) in shallow aquifer at the groundwater discharge area (close to coast line), predominates Na-Cl type (P-03 and P-05), with remarkable influence of Na+ and Cl−. In the basin, the rise of the Na+ content and gradual Ca2+ decrease occurs due to the ion exchange phenomenon caused by the contact of groundwater with clay minerals. Near to the coast, the great enrichment of Na+ and the Na-Cl facies is associated to the presence of salt deposits from ancient sea evaporation, as suggested by Pinto et al. (2006), as well as due to seawater encroachment. The Cl/Br ratio values are presented in Table 2. The meteoric water sampled displayed Cl/Br ratio of 74, value expected by atmospheric precipitation (between 50 and 150 – Davis et al., 1998). The Macacu and Alluvial Lacustrine Aquifers presented large 8

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Fig. 5. Diagram Chloride versus major ions.

Fig. 6. Piper-Hill Diagrams.

variation of the Cl/Br ratio, ranging from 122 to 1420 and from 158 to 1071, respectively. For Fluvial Marine Aquifer, the Cl/Br ratio presented was a short range of values, from 274 to 595. Relevant variations of Cl/Br ratio versus Cl− concentrations are verified for these data and could indicate different sources of salinity. Concerning the stable isotopes data from Macacu Basin granular aquifers, the δ2H ranged from -36.34 to -19.77‰ V-SMOW and 18 δ O from -5.92 to -0.08‰ V-SMOW while the deuterium excess (d-excess) was between 1.72 and 11.8‰ (calculated as d= δ2H – 8δ18O). The Fig. 7 shows the relationship between δ2H and δ18O from the groundwater samples and they show arrangement on the Global Meteoric Water Line (GMWL) given by the equation δ2H = 8δ18O + 10‰ (Craig, 1961). The local meteoric water line, based on the data from IAEA given by δ2H = 8.08δ18O + 12.63‰ (n = 132, monthly average from 1961 to 1985) was also plotted together with GMWL. It could be noticed that LMWL is very similar to the GMWL and the most groundwater samples have the same trend. The most d-excess values found in the study area (Table 2) were < 10. These facts corroborate the hypothesis of groundwater recharge for all area (considering the granular aquifers). The two rainwater samples from November and December 2009 have less fractioning, pointing out high evaporation rate of the sampling period.

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Fig. 7. Graphic of δ18O X δ2H in natural waters of Macacu Basin.

5. Discussion Regarding the influence of saline intrusion, according to IGME (2009), in coastal aquifer with natural conditions, there is the contact between fresh groundwater and saltwater (considering two immiscible solutions), which form a transition zone that mix both solutions progressively by diffusion processes. The mixing zone can move according to reducing of fresh groundwater flow toward sea and/or a variation of the permeability from the aquifers systems according to the lithological heterogeneity, tidal frequency and oscillations (Sanders et al., 2012). Because it is a transition environment, with similar altimetry to sea level and the mangrove area, it was assumed significant influence of seawater upon fresh groundwater in P-05, presenting close relationship to the tidal variation, which influence the EC values and water table variation. In order to verify this relationship, the Fig. 8 show temporal graphs for P-05 and P-01C (close to coastline) considering the water level and EC. It is possible to notice the water level and EC maximum and minimum values in P-05 are well correlated and could be associated to the tidal oscillation, the opposite behavior of P-01C, showing the P-05 is located on the mixing zone between fresh groundwater and seawater intrusion.

5.1. The controlling of ionic behavior through the hydrogeochemical modeling The hydrogeochemical modeling for the studied area was carried out by PHREEQC (Parkhurst and Appelo, 1999), considering the physicochemical parameters and the saturation index (SI) data from the different aquifers. Regarding the aquifers chemical and mineralogical composition, the chosen minerals for the modeling were calcite, dolomite, gypsum and halite; the carbonate minerals should come from both the seawater influence and weathering reactions from aquifer materials; halite could come from the aquifer materials as well as from seawater influence; the sulfate salt also could come from both seawater influence and from the sulfuric gas generation by the organic matter decomposition. Fig. 9 examines the behavior among the main physicochemical parameters (EC, pe and pH) and the Fig. 10 compares these physicochemical parameters with minerals SI. Observing the graphs A and B (Fig. 9), it is possible to notice the well-marked behavior of EC in each studied aquifer system, namely, the Fluvial-Marine Aquifer, with the highest EC values, followed by the AlluvialLacustrine Aquifer, the Deep, Medium and Shallow Macacu Aquifers samples. Considering all data, there is no significant correlation between EC and pH (Fig. 9 - graph A), however, the pe has evident negative correlation with EC and pH (Fig. 9 - graphs B and C), suggesting oxidation/reducing process, mainly along the Deep Macacu Aquifer, which displays markedly two main groups, one with 10

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Fig. 8. Water level X EC (P-01C and P-05) compared to the tidal variation of Guanabara Bay.

Fig. 9. Diagrams of physicochemical parameters.

higher pe and lower pH values, represented by the well P-02B, and other (most samples), with lower pe and higher pH values (P-01 A, P-02 A and P-03 A). That behavior difference could be due to the influence of a local structure (lineament, Fig. 1) close to the location of P-02B, which favor groundwater circulation and mixing among porous aquifers (even the fractured aquifer in basement rocks), conditioning oxidation and dilution processes (decreasing of EC and pH values). The other group (composed by P-01 A, P-02 A and P03 A) has no influence from any structure and presents reduced conditions, higher EC values probably due to the larger residence time of groundwater, triggering the rise of pH values. The Shallow Macacu Aquifer samples present low physicochemical parameters variations, mainly for EC and pH, because of the direct influence of rainwater and the poor composition of the aquifer material. The Fluvial-Marine Aquifer samples (P-05) also presents low oscillations of physicochemical parameters although it has the highest EC values (due to the inflow of marine water) and low pe (because the reduced mangrove environment). The relative lower pH values could be explained by the rapid local rainfall (see the δ18O content in Table 1), which should dilute the groundwater and oxidize the mangrove sediment (presence of H2S and microcrystalline pyrite), increasing the hydrogen ions concentration (< pH). The Medium Macacu Aquifer samples could be also separated in two groups, one with P-04 A samples, presenting higher EC and pH values and lower pe ones; and the other group with P-01B samples, presenting the opposite behavior from P-04 A. In this case, the behavior difference between the two groups is the influence of residence time on the well P-04 A, giving high values of EC and pH, and due to the well depth (˜ 90 m), where it has little water circulation and, consequently, low pe values. The Alluvial-Lacustrine Aquifer samples are well represented by all analyzed physicochemical parameters, also displaying two main groups. The first one with high pH and pe and median EC values (P-03B), and other with low pH and pe and high EC values (P11

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Fig. 10. Saturation index (SI) versus electron activity (pe).

01C). As before commented, P-01C should have influence of older coastal sediments salts present in the aquifer materials, besides the significant presence of organic matter, corroborating the physicochemical parameters behavior at this well, while in P-03B, located at the basin border, has the opposite behavior. Observing the Fig. 10 and considering all samples, the SI for calcite presents the most samples in equilibrium (SI = 0) and in saturation (SI > 0) from Deep Macacu Aquifer, showing that significant residence time of groundwater (weathering process) contributes more than salt intrusion for that mineral formation (samples from Fluvial-Marine Aquifer). Presenting the same behavior trend of calcite, the SI for dolomite also shows most of Deep Macacu Aquifer samples in equilibrium and in saturation with the solution, but some samples from Medium Macacu, Alluvial-Lacustrine and Fluvial-Marine Aquifers are found close to the equilibrium. The SI for gypsum displays all samples in undersaturation (SI < 0) with the solution, showing few samples of Fluvial-Marine and Alluvial-Lacustrine Aquifers a little closer to the equilibrium zone. Possibly this mineral could get the equilibrium in groundwater closer the coastline (higher influence of seawater intrusion). It is worth to notice that halite shows the lowest SI values among the selected minerals for geochemical modeling (all samples undersaturated, SI < 0). The physicochemical parameters behavior in each aquifer body exerts influence on the SI behavior of the chosen minerals. Once more, considering all samples, it is noticed the EC has moderate positive correlation with SI of the four chosen minerals; the pH has good positive correlation with only the carbonate minerals, while pe has moderate negative correlation with the carbonate minerals as well. Those SI data suggest the carbonate minerals get the equilibrium at high pH and EC and low pe, corroborating the geochemical processes described for most samples from Deep Macacu Aquifer and some samples from Fluvial-Marine, Medium Macacu and Alluvial-Lacustrine Aquifers. In other words, the calcite and dolomite will prevail in case of 1) high residence time of groundwater in the aquifer; 2) groundwater close to mixing zone of salt wedge; 3) presence of older coastal sediments in the aquifer matrix. For gypsum, only EC has moderate correlation with SI, highlighting samples of Fluvial-Marine Aquifer, which are the closer samples to the equilibrium zone. For halite, it has moderate correlation with EC, showing its highest SI values associated to the Fluvial Marine and Deep Macacu Aquifers, which wells are located closer to the coast line (P-04 and P-05). Observing the Fig. 10, it is possible to notice the increasing of gypsum SI in Fluvial-Marine Aquifer, supporting the hypothesis of gypsum equilibrium under marine influence (Ayora et al., 1995). Moreover, gypsum tends to reach equilibrium in mangrove environment due to higher sulfate availability (as product of mangrove sediments oxidation or present in seawater). Although the high concentrations of Cl− in the Fluvial Marine and Deep Macacu Aquifers, the geochemical modeling showed no equilibrium with halite. It could be caused by the dilution of seawater encroachment through the great freshwater availability (groundwater and surface water) and also due to ion exchange of Na+ with clay-minerals (Tertiary and Quaternary sediments). 5.2. Chloride/Bromide ratios and isotopic approach Considering the seawater intrusion is the responsible to affect only Fluvial-Marine Aquifer and its EC increasing, significant concentrations of Cl− and Na+ are observed in other aquifers systems and could have the same origin (Yamanaka et al., 2011). Therefore, the Cl/Br ratio and the stable isotopes data were used in order to establish the salinity origin in the aquifers systems of the Macacu Sedimentary Basin. The Cl/Br ratio values, Cl− concentrations and data of oxygen and hydrogen isotopes were plotted in graphs (Fig. 11), pointing 12

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Fig. 11. Cl/Br ratio associated with chloride concentration in Macacu Basin and δ18O and δ2H versus CE in groundwater.

out 4 different groups regarding the salinization and origin of groundwater: 1) Group G1 is constituted by recharge waters which have Cl/Br ratio values between 122 and 539 and Cl− concentrations lesser than 19 mg l-1. Concerning the light waters from this group, characterized by δ18O ranging from -5.92 and -4.63‰, δ2H from -36.34 to -27.36‰ and EC values ranging from 176 to 376 μS cm-1, suggest less evaporated groundwater (light isotopes enrichment) and relevant input from meteoric water. The wells P-02 A, P-03 A and P-01 A from Deep Macacu Aquifer and P-01B from Medium Macacu Aquifer represent this group and suggest the most recharge water come from the basin headboard come from the faulting and fracturing structures of basement rocks (fractured aquifer). 2) Surrounding the P-02, the samples of P-02B and P-02C, respectively Deep and Shallow Macacu Aquifer, presenting higher δ18O values (between -4.42 and -3.64‰), higher δ2H values (ranging from -22.77 to -26.03‰) and EC ranging from 71 to 366 μS cm−1 (Table 2). Those data can indicate mixing through vertical flow with high residence time waters from Rio Vargem Member. 3) Group G2, formed by groundwater with Cl/Br ratio values between 1007 and 1420 and Cl− concentrations ranging from 122 to 178 mg l-1, represented by multilevel well P-04, which is located on the Alluvial-Lacustrine and Macacu Aquifers. The increase of Cl/Br ratio values in this group is due to the groundwater flow path reaches the Rio Vargem Member from Macacu Formation, which presents brackish water environment sediments. Davis et al. (1998) suggested Cl/Br ratio values between 1000 and 10,000 are associated to groundwater affected by aquifers containing halite. Besides this fact, there is the influence of seawater encroachment, justifying the high values for δ18O (-0.08‰) and δ2H (-20.28‰) associated with high EC value (1120 μS cm-1). 4) Group G3 is constituted by groundwater with low Cl/Br ratio values (from 158 to 591) and high Cl− concentrations (from 443 to 573 mg l-1), representing samples collected in the Alluvial-Lacustrine Aquifer (P-01C). The high Cl− concentrations observed in this well probably be related to “in natura” domestic sewage releasing in Caceribu river. On the other hands, the high Br− concentrations could be related to organic matter in shallow aquifers (Davis et al., 1998). This group is characterized by low δ18O values (ranging from -5.52 to -5.18‰), δ2H (from -34.15 to -32.53‰) and EC values (from 1564 to 2302 μS cm-1). The EC values and light isotopic ratios corroborates hypothesis about the influence from the Caceribu river, naturally light isotopes enriched, which is broadly impacted by domestic sewage. 5) Group G4 is formed by groundwater with Cl/Br ratio values between 274 and 595 and Cl− concentrations ranging from 803 to 1243 mg l-1. This group represents the Fluvial-Marine Aquifer from the mangrove area (Guapimirim EPA). This region has clayey sediments enriched in organic matter and, as well as group G3, also has significant Br− concentration. Nevertheless, in this area, the seawater intrusion preserves high values of Cl/Br ratio. This group displays an enrichment in δ18O (ranged -4.06 to -3.91‰) and δ2H values (ranged -21.58 to -19.77‰) and the highest values for EC (between 5348 and 5651 μS cm-1). The higher content for δ18O and δ2H in this area is due to the rapid local rainfall and/or the mixing of groundwater and seawater intrusion, characterizing the groundwater discharge zone.

6. Conclusion Although the relative small area (375 km2), the aquifer system from Macacu Sedimentary Basin presents a wide range of salinity, which reflects in diversified geochemical behaviors. The hydrochemical evolution of groundwater in the Macacu Sedimentary Basin is characterized by a gradual evolving from Ca-HCO3 facies in the recharge areas (in the basin border toward the crystalline basement) to Na-HCO3 facies in the central region and after to Na-Cl facies, near the coast line. Therefore, it is evident a Ca decrease concomitant to a Na increase and it is due to the ionic exchange between groundwater and aquifer matrix. This fact is corroborated by the PHREEQC modeling, which showed that high pH and low pe values conditioning the main processes controlling the 13

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hydrogeochemical evolution of groundwater in that region. The groundwater from the study area could be distinguished in four different groups, regarding the Cl/Br ratio values, which suggests the salinity origin: i) rapid recharged groundwater, which Cl/Br ratio values are similar to rainwater; ii) discharge area groundwater, which are affected by salts dissolution (halite) from brackish water environment deposits; iii) groundwater with high Cl− concentrations and also significant Br− concentrations due to the influence of organic matter deposits and; iv) groundwater with highest Cl− concentrations and highest Cl/Br ratio due to the seawater intrusion. Based on the hydrodynamics and stable isotopes data, the groundwater flow model at Macacu Basin points out recharge areas on P-01, P-02 and P-03 which represent waters from Deep Macacu Aquifer, suggesting different origins and residence times. Therefore, the Macacu Aquifer System has direct recharge by rainwater as well as by indirect recharge from fractured aquifer (crystalline basement), causing the mixing among the aquifers systems. Lastly, the basin discharge zone is found in P-04 area and Guapimirim EPA (well P-05). Conflict of interest The authors of the following paper entitled: “origin of salinity and hydrogeochemical features of porous aquifers from northeastern Guanabara bay, Rio de Janeiro, SE - Brazil” claim for appropriate action has no conflicts of interest that may interfere with the impartiality of scientific work. Acknowledgements This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001. The authors would like to thank the Instituto Nacional de Ciência e Tecnologia (INCT-TMCOcean 573601/20089). The authors are also grateful for the support of the FEEDBACKS-PRINT-UFF Project (grant CAPES 88887.310301/2018-00). E. Silva-Filho is senior researcher of the National Council for Research and Development (CNPq, Brazil) and the Foundation for Research Support of the State of Rio de Janeiro (FAPERJ E-26/203.037/2017). Appendix A. Supplementary data Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.ejrh.2019. 100601. References Alcalá, F.J., Custodio, E., 2008. La relacion Cl/Br como indicador del origem de la salinidad en algunos acuíferos de España y Portugal. Groundwater flow understanding, from local to regional scale. In: 33th International Congress of Hydrogeologists Association – ALHSUD, 2008 2008, 4 p. Alley, W.M., 1993. Regional Ground-Water Quality. Van Nostrand Reinhold, New York 634p. Almeida, F.F.M., 1977. O Cráton do São Francisco. Rev. Bras. Geosci. 7, 349–364. Almeida, F.F.M., 1981. O Cráton do Paramirim e suas relações com o do São Francisco. 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