Short communication

Concentrations of Rare Earth Elements and other

Chemical Elements in Sediments of Rivers throughout
Chile.

Keywords
river, emerging technologies, sediments, freshwater ecosystem, Rare earth elements

Abstract
The increase in demand for emerging technologies has also increased the presence of rare earth
elements and other lesser-known elements in the environment that were previously stable in the
earth's crust. The aim of this study was to determine the current status of five rare earth elements
such as cerium (Ce), lanthanum (La), neodymium (Nd), praseodymium (Pr) and yttrium (Y), and
barium (Ba), niobium (Nb), rubidium (Rb), thorium (th) and zirconium (Zr), in superficial sediments
from rivers of northern, central and southern Chile. Data showed that the order of abundance of
elements in the river sediments was Ba > Nd > Pr > La > Ce > Zr > Rb > Y > Th > Nb. We found
higher Ba, Ce, La, Nd and Pr contents in northern and central Chile. Our findings showed that
probably these chemical elements are adsorbed into sediments, which could facilitate remobilization to
the water column, thus being more bioavailable to biota. Considering that rivers of northern and central
Chile are usually used for human consumption and irrigation purposes, further studies to understand
the processes involved in the recycling of elements in the watersheds are necessary. Our results may
serve as a basis for environmental impact studies that are required by the Chilean legislation before
any productive investment.

Authors
Dr. José E. Celis
Department of Animal Science, Facultad de Ciencias
Veterinarias, Universidad de Concepción, Chile

Dr. Winfred E. Espejo

Department of Soils and Natural Resources, Facultad de
Agronomía, Universidad de Concepción, Chile

Dr. Gustavo Chiang

Ecology & Biodiversity Department & Sustainability Research
Centre, Facultad de Ciencias de la Vida, Universidad Andrés
Bello, Chile

Dr. Christopher Celis

Comisión Chilena de Energía Nuclear, Chile

Dr. Paulina Bahamonde

Laboratory of Aquatic Environmental Research, Centro de
Estudios Avanzados - HUB Ambiental UPLA,, Universidad de
Playa Ancha, Chile

Explanation letter
ANSWERS TO THE REVIEWERS

Ref. PJOES-00134-2022-01
“Concentrations of Rare Earth Elements and other Chemical Elements in Sediments of Rivers
throughout Chile”
To the Editor: all changes made in the manuscript revised version are highlighted in yellow.

Reviewer #1:
The study is quite comprehensive for its region. I think that some of the points I have mentioned below
should be explained.
Query: How was the accuracy of the analyzes determined?
Answer: OK. We added the following sentence in page 5: “The precision and accuracy were verified
by means of international reference standards such as GSS-5, GSS-7, GXR-6 and GSR-3 [18], being
the precision < 2% and accuracy within 1–5%.”
Query: I think that the second study would be a more comprehensive study if the samples of the last 3
years were collected and the average was given.
Answer: We agree with the reviewer.

Reviewer #2:
Query: First, I suggest to the authors a review in language.
Answer: This manuscript was checked by Ms. Diane Haughney, who is a native English person, and
so many thanks to her are mentioned in the Acknowledgments section.
Query: In the summary, I recommend that the authors better define the objective of the work. It is not
presented clearly.
Answer: OK. We added the following sentence in the Abstract: “The aim of this study was to determine
a baseline for cerium (Ce), lanthanum (La), neodymium (Nb), praseodymium (Pr), yttrium (Y), barium
(Ba), niobium (Nd), rubidium (Rb), thorium (th) and zirconium (Zr) in superficial sediments from rivers
of northern, central and southern Chile.”
Query: The purpose of the manuscript does not correspond to the title. The authors propose to
determine baseline levels for rare earth elements and some heavy metals, however the title is referring
only to the concentrations that were determined for the study area.
Answer: OK. We changed the title to “First Report of Rare Earth Elements and Other Chemical
Elements in Sediments of Rivers throughout Chile”

Materials and methods

River selection and sampling
Query: The authors did not mention the number of samples for each river, I propose adding more
information about how the samples were sampled. If they were carried out along all the rivers from the
source to the mouth or if they were divided in the upper, middle and lower rivers subdivisions and
mainly in the number of samples for each river. And even if they were surface or subsurface samples,
in case of subsurface, if they were stratified or not.
Answer: The number of samples for each river is denoted as (n=3) in page 4, where we added that the
part of the river sampled was in the middle. Regarding the question if they were surface or subsurface
samples, in the same paragraph of page 4 it is stated that was superficial.
Query: I suggest that the authors add information about the local geology that gives more ground for
the reader to know the region of study, as well as, in the discussion of the results.
Answer: OK. We added more information of the areas studied, as is noted in page 3 and 4 (highlighted
in yellow).
Query: I also submit authors to add more graphic elements in Figure 1, such as the hydrography, the
Pacific Ocean, the countries bordering Chile, as well as the position in South America. Theses addition
of cartographic and graphic elements will facilitate the understanding of the map.
Answer: OK. We included additional information in Fig. 1.
Query: The purpose of the manuscript is to determine baseline values for the elements studied.
However, the authors did not mention any methodology for calculating baseline levels. I suggest
authors to add the methodology for the baseline calculation and the background values as well.
Answer: Our study aims to see the current environmental status of the elements, as a first report,
which can serve as a basis for future studies that evaluate anthropogenic impacts in the face of the
increasing use of these elements. That was the reason for modifying the title to avoid confusion.
Query: In the results and discussion, I suggest to the authors a detailed review, as there are repeated
sentences throughout the text.
Answer: OK. We revised the text in such as a way not to repeat any sentences among the
paragraphs.
Query: Regarding of subitem that say about the comparisons of concentrations with other locations, it
will be more interesting for the authors to make comparisons with the baseline and background levels
worldwide, such as those of Turekian and Wedepohl (1961) and others. Those paper mentioned by
the authors were recorded in environments with different geological and geochemical characteristics,
that difficult comparisons. It is necessary that they are similar geological environments to the study
area, thus, it facilitates the comparison with the study area.
Answer: Although these foreign studies are of different geological and geochemical characteristics
than our study, the comparisons we believe are valid in the framework of our objective, which is to
reflect the current status of rare earth element levels in surface river sediments that have been little
studied. Comparisons between the different geographic regions of Chile present the same difficulty,
either because they have very different geological, climatic and hydrological characteristics, which is
stated in page 7, just before the conclusions.
We added the following sentence in page 7: “When comparing with background earth´s crust levels
reported worldwide (Lide, 2009), the maximum Ce, La, Nd and Pr levels found in the present study are
5, 7, 13 and 53 times higher, respectively, whereas the Y contents are 0.8 times lower. On the other
hand, the minimum Ce, La, Nd and Pr levels are 2, 3, 5, 26 times higher whereas our Y levels are 0.2
times lower than those Earth´s crust levels.”
In any case, our results may serve as a basis for environmental impact studies that are required by the
Chilean legislation before any productive investment would be implemented in the territory. Moreover,
in the present study we are just issuing data that may serve to open the interest of the scientific
community, and thus they can investigate in the behavior of the REE between regions with similar
characteristics.
Query: Generally, for the analysis of rare earth elements, normalization with the chondrite values is
used. I suggest that the authors review this analysis used to make figure 2 of the manuscript, as well
as the use of this normalization with the chondrite by other authors.
Answer: The figure 2 was just set in order to see any uniformity among rare earth elements. Rare
earth normalization to chondrite are widely used in Geology to show some possible depletion or
enrichment in light rare earth elements relative to heavy rare earth elements. We believe that this is
beyond the focus of this study, and for that reason it was not considered here. Our findings are the
first report on rare earth elements in sediments of rivers along Chile. Of course, further studies might
consider this important issue.
Query: The authors mentioned that Spearman correlations were performed with all the elements
analyzed, however, the authors did not show any value or table of this correlation. I suggest authors to
analyze this information more carefully, adding these values throughout the text or in a table for better
visualization by the reader.
Answer: OK. We are sorry for omitting that valuable information in the original manuscript. Now, we
included the Table 5 with the Spearman coefficients of all the elements analyzed.
Query: The authors mention that there are several urban agglomerations along the rivers. I suggest
the authors add the main urban agglomerations and their size to the location map.
Answer: OK. We added in the text (Materials and Methods) more information describing anthropogenic
sources along the rivers.
Query: The manuscript is extremely relevant to the scientific community and with the points to be
observed and the suggested modifications, mainly in the methodology, it will be an important tool in
the identification and distribution of metal contamination for the region.
Answer: We agree with the reviewer. This manuscript pretends to be a reference for further studies for
the region, where mining activities are crucial and relevant.
Response to Reviewers.docx
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1 1

2 First Report of Rare Earth Elements and Other Chemical Elements in Sediments of Rivers
3 throughout Chile

4 José E. Celis1, Winfred Espejo2*, Gustavo Chiang3, Christopher A. Celis4, Paulina Bahamonde5,6

5 1
Department of Animal Science, Facultad de Ciencias Veterinarias, Universidad de Concepción, Av.
6 Vicente Méndez 595, Chillán, Chile
7 2
Departamento de Suelos y Recursos Naturales, Facultad de Agronomía, Universidad de Concepción,
8 Casilla 537, Chillán, Chile
3
9 Ecology & Biodiversity Department & Sustainability Research Centre, Facultad de Ciencias de la
10 Vida, Universidad Andrés Bello, Santiago, Chile
11 4
Comisión Chilena de Energía Nuclear, Nueva Bilbao 12501, Las Condes, Santiago, Chile
5
12 Laboratory of Aquatic Environmental Research, Centro de Estudios Avanzados - HUB Ambiental
13 UPLA, Universidad de Playa Ancha, Valparaíso, Chile
6
14 Millennium Nucleus INVASAL
15 *e-mail: winfredespejo@udec.cl

16 Abstract
17 The increase in demand for emerging technologies has also increased the presence of rare earth
18 elements and other lesser-known elements in the environment that were previously stable in the earth's
19 crust. The aim of this study was to determine the current status of five rare earth elements such as
20 cerium (Ce), lanthanum (La), neodymium (Nd), praseodymium (Pr) and yttrium (Y), and barium (Ba),
21 niobium (Nb), rubidium (Rb), thorium (th) and zirconium (Zr), in superficial sediments from rivers of
22 northern, central and southern Chile. Data showed that the order of abundance of elements in the river
23 sediments was Ba > Nd > Pr > La > Ce > Zr > Rb > Y > Th > Nb. We found higher Ba, Ce, La, Nd
24 and Pr contents in northern and central Chile. Our findings showed that probably these chemical
25 elements are adsorbed into sediments, which could facilitate remobilization to the water column, thus
26 being more bioavailable to biota. Considering that rivers of northern and central Chile are usually
27 used for human consumption and irrigation purposes, further studies to understand the processes
28 involved in the recycling of elements in the watersheds are necessary. Our results may serve as a basis
29 for environmental impact studies that are required by the Chilean legislation before any productive
30 investment.
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31 2

32 Keywords: Rare earth elements, trace elements, sediments, river, emerging technologies, freshwater
33 ecosystem

34 Introduction
35 Rivers have chemical, physical and biological features that provide habitat for different
36 components of aquatic biota, such as algae, benthic invertebrates, and fish [1]. Moreover, due to the
37 unidirectional nature of rivers, these aquatic systems play a fundamental role in the transport of a
38 multiplicity of elements derived from natural processes and anthropogenic activities, where sediments
39 are crucial as they participate in the adsorption and resuspension-deposition of a wide variety of
40 elements [2]. In this regard, chemical elements can interact strongly with river sediments through
41 various processes, and their concentrations can reveal the degree of anthropogenic presence and
42 pressure in the watershed [3]. For that reason, chemical elements are usually parameters selected for
43 monitoring programs due to their toxicity, bioaccumulation and persistence in the natural environment
44 [4].
45 The rivers in Chile flow from the Andes Mountains to the Pacific Ocean, and their hydrological
46 patterns vary spatially due to climate, the presence of glaciers, lakes or volcanoes, the slope of the
47 terrain, altitude, geology, land use and water consumption, with these three last factors having the
48 greatest influence on water quality, along with the amount and quality of the transported sediments
49 [5, 6]. As a consequence, river sediments are excellent indicators of chemical element pollution [7] as
50 such chemicals will be adsorbed to the sediment, depending on the physical-chemical properties of
51 the element, natural and anthropogenic factors, and the nature of the sediments [8]. Among the main
52 anthropic activities affecting Chilean Rivers and sediment transportation is the modification of the
53 hydrological regime due to channeling, damming of rivers, extraction of water for irrigation,
54 extraction of aggregates, replacement of native forest by artificial forest, and alteration of the
55 physicochemical quality of the water, thus affecting the habitat of the biota [6]. The most common
56 anthropogenic actions resulting in river contamination are wastewater from households and industries,
57 mining tailings, pulp/paper mill wastewater, and agricultural practices [5, 9].
58 The presence of metals in Chilean river sediments has been associated with the presence of
59 metallogenic strips in the upper part of the Andes Mountains as a natural factor, and to the extractive
60 mining activities that take place mainly in the northern part of the country, whereas impacts of the
61 agricultural practices and urban development can be found in the central valley, while southern Chile
62 presents low human presence and impacts [10].
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63 3

64 To develop guidelines for environmental protection of rivers, it is necessary to establish chemical

65 element concentrations in sediments at baseline to distinguish natural source levels from those from
66 anthropogenic sources [11]. Recently, new potentially toxic elements, which had been usually stable
67 in the Earth’s crust, have emerged as consequence of the increase in mining related to the development
68 of modern technologies, such as cell phones, portable computers, biomedicine, and photovoltaic cells
69 [12, 13]. Among them are some rare earth elements such as Ce, La, Nd, Pr or Y, and other lesser-
70 known elements such as Ba, Nb, Rb, Th or Zr, which are increasingly being released into the
71 environment, with a potential change of natural biogeochemical cycles and possible severe effects on
72 wildlife and the natural environment [14-16]. In Chile, river rare earth elements pollution is an issue
73 not considered yet in public management. To our knowledge, no data are available on the distribution
74 of these less-studied chemical elements in the sediment of the Chilean Rivers. Consequently, the aim
75 of this study was to determine a current status for ten little studied chemical elements (Ba, Ce, La, Nb,
76 Nd, Pr, Rb, Th, Y, Zr) to establish a tool for future monitoring programs.

77 Materials and Methods

78 Selected rivers and sampling
79 During 2019-2020, we collected sediment samples (~50 grams) from several rivers throughout
80 Chile (Fig. 1). The rivers in northern Chile (A) show a typical nival regime and the basins are
81 characterized by major mining activities and the presence of volcanoes. In central Chile (B), river
82 discharges show mixed regimes, which depend on snow and rain precipitation, with strong influence
83 of volcanoes, urban development and agricultural activities. In the southern area (C), rivers show a
84 strong pluvial regime, and they are located in one of the most austral regions of South America,
85 considered as a pristine area with no mining or volcanic activity.
86 The Loa River is the longest river in Chile (440 km) and flows through the Atacama Desert from
87 its source in the Andes Mountains to the Pacific Ocean; it is of great importance in the development
88 of human life, such as Calama, the main city with a population of more than 140,000 inhabitants,
89 mainly dedicated to the mining industry; the Loa River supplies water to the towns in the area and to
90 the mines located in the area, including Chuquicamata, the largest open-pit copper mine in the world,
91 and the cultivation of various vegetables for local consumption. The Elqui River is located 470 km
92 north of Santiago, Chile; it rises in the Elqui valley at 815 m.a.s.l. and flows into the Pacific Ocean
93 near the city of La Serena; one of its tributaries is the Turbio River. The Choapa River is a natural
94 watercourse, whose basin extends from the watershed in the Andes Mountains to its mouth at the
95 Pacific Ocean, receiving the waters of several tributaries. The Maipo River is a watercourse that flows
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96 4

97 through the Metropolitan Region (highest population density of Chile, where the capital city of
98 Santiago is located) and then through the Valparaíso Region, reaching the Pacific Ocean; because of
99 the large amount of population and productive activities in its basin, it is one of the most important
100 rivers of Chile. The Maipo River is located in an area where there are different deposits in the geology
101 of the Cajón del Maipo, with fluvial, fluvioglacial and alluvial deposits strongly linked to the
102 formation of terraces throughout the Cajón. The Trancura River is a watercourse that flows in the
103 Araucanía Region, which originates in the Quillelhue Lagoon and flows into the Villarrica Lake. The
104 Correntoso River is a watercourse that originates from other tributaries in the Araucanía Region,
105 which flows into the Pucón River. The Correntoso and Trancura rivers are located in an area that
106 represents the evolution of the South American southwest margin, from the Mesozoic to the Holocene.
107 The Marchant River is located in the Aysén Region (300 km south of Puerto Montt) is influenced by
108 the Melimoyu volcano, and it originates from snow and rainfall, flowing into the Pacific Ocean. The
109 Bronce, Robalo and Akika rivers, which flows into the Beagle Channel, are located on Navarino
110 Island, Tierra del Fuego, Southern Chile, with the absolute absence of volcanoes. The relief of
111 Navarino Island is of subglacial origin, where the summits rarely exceed 1,000 m.a.s.l., with the
112 Dientes de Navarino peak being the highest elevation summit on the island, reaching 1,118 m.a.s.l.
113 At all sites, superficial sediment samples (~20 cm depth) were collected in the middle part of the
114 rivers by means of a pre-cleaned plastic shovel (n=3 per site), and then stored at -20°C in clean
115 polypropylene bags (Whirl-Pak®) until their arrival at the laboratory

116 Sample preparation and analysis

117 In the laboratory, all samples were freeze-dried until dry masses were constant, and then
118 homogenized to a fine powder using a glass mortar previously cleaned with a 2% Conrad solution
119 (Merck) for 24 h, washed with deionized water + 1M HCl, and then rinsed with distilled water [17].
120 Afterwards, the samples were heated (oven at 100 °C for 12 h) to remove adsorbed water prior to
121 analysis [18]. Then, the samples were analyzed for chemical elements at the Analytical Laboratory of
122 the Faculty of Veterinary Sciences, Universidad de Concepción (Chile), using a portable battery-
123 operated energy dispersive X-ray fluorescence spectrometer (Thermo Scientific Niton XL3t 950 He
124 GOLDD+). The instrument was set up with the instrument tip up on a shielded laboratory test stand,
125 which was remotely operated. The precision and accuracy were verified by means of international
126 reference standards such as GSS-5, GSS-7, GXR-6 and GSR-3 [18], being the precision < 2% and
127 accuracy within 1–5%.
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128 5

129 Data were statistically analyzed by means of nonparametric statistical methodologies because of
130 the assumptions of normality and homoscedasticity were not met. Differences between chemical
131 element concentrations were assessed by means of the Kruskal–Wallis analysis of variance and
132 Mann–Whitney U tests. Post hoc tests were carried out by means of Kruskal–Wallis analyses, using
133 the critical differences of mean rank. Spearman rank correlation coefficients were calculated between
134 chemical element levels. A significance level of p ≤ 0.05 was considered to indicate statistical
135 significance. Data were analyzed by using the R program.

136 Results and Discussion

137 Chemical element concentrations by geographical locations
138 For the detected elements found in northern Chilean rivers (Table 1), the highest concentration
139 corresponded to Ba detected in the sediments of the Turbio River (654.73 µg/g), whereas the lowest
140 levels were for Nb in the Loa River (3.47 µg/g). For central Chilean rivers (Table 2), the highest levels
141 of the chemical elements corresponded to Nd found in the sediments of the Correntoso River with
142 426.98 µg/g, whereas the lowest contents corresponded to Nb in the sediments of the Trancura River
143 (2.69 µg/g). In southern Chile (Table 3), the highest levels of the chemical elements corresponded to
144 Ba in the sediments of Marchant River (457.59 µg/g), and the lowest to Nb (2.91 µg/g) in the
145 sediments of Bronce River. For the detected elements found from northern Chilean rivers (Table 1),
146 the highest concentration corresponded to Ba detected in the sediments of Turbio River (654.73 µg/g),
147 whereas the lowest levels for Nb in the Loa River (3.47 µg/g).
148 Across Chilean rivers studied here (Table 1, 2 and 3), the highest means contents of Ba, Ce, La
149 and Nd were found in the sediments of Loa River in northern Chile, as well as the highest mean levels
150 of Rb were found in Turbio River. The highest mean values of Nb, Pr, Y and Zr are in the sediments
151 of Marchant River (southern Chile), while the highest mean Th contents were found in the sediments
152 of Robalo River. The highest concentrations of the lanthanide group (Ce, La, Nd, and Pr) and Ba in
153 the river sediments along Chile may be associated with the presence of volcanoes in the regions where
154 the Loa River, Turbio River, and Marchant River are located. The presence of Ba and rare earth
155 elements (such as Ce, La and Nd) could be linked to volcanic activity [19]. Additionally, there is
156 evidence that mining activities related to copper and molybdenum tend to impact watercourses with
157 rare earth elements [20, 21], a situation observed in northern Chile which has a generally strong
158 copper-mining activity. On the other hand, the Robalo, Ukika and Bronce rivers presented lower
159 concentrations of Ce, La, Nd and Pr, which could be explained by the fact that these rivers are located
160 in an area with no volcanic activity and with little anthropic intervention.
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162 Comparison to worldwide studies

163 To date, there are few studies on the same chemical elements studied here at global level, thus
164 making it difficult to discuss our results. The comparison to other previous studies elsewhere revealed
165 that the highest mean concentrations of Ba (591.7 µg/g, Turbio River), Ce (249.5 µg/g, Loa River),
166 La (251.63 µg/g, Loa River), Nd (453.2 µg/g, Loa River), Pr (432.95 µg/g, Marchant River) and Th
167 (16.68 µg/g, Robalo River) are higher than those levels reported in the sediments of rivers of the
168 northern hemisphere such as Mississippi, Nile, Rhine or Volga [22].
169 According to Table 4, our maximum Ba levels are lower than those levels reported in stream
170 sediments of the Varzob River, Tajikistan, while higher than those levels found previously in
171 sediments of rivers from Brazil and Chile. Our maximum Ce levels are lower than those levels
172 reported in south-west England, but higher than those levels reported in river sediments from Korea,
173 China, Mongolia and Tajikistan. For La, the maximum levels are lower than those levels reported
174 from England, but higher compared to the rest of rivers listed. For Nb, our maximum levels are around
175 half of those levels found in river sediments of Brazil. For Nd and Pr, our maximum values are higher
176 than those levels reported in sediments of rivers from the northern hemisphere (Table 4). For Rb, our
177 maximum levels are lower than those levels reported from Tajikistan and Brazil, whereas are higher
178 than those levels reported previously from Chile. For Th, our maximum levels are higher than those
179 levels reported from Brazil. For Y, our maximum levels are lower than those levels reported from
180 England, Korea, China and Brazil, whereas are higher than those Y levels found in Mongolia. Finally,
181 our maximum Zr levels are 2.3 times lower than those levels found in stream sediments of the Varzob
182 River, Tajikistan. When comparing with background earth´s crust levels reported worldwide [28], the
183 maximum Ce, La, Nd and Pr levels found in the present study are 5, 7, 13 and 53 times higher,
184 respectively, whereas the Y contents are 0.8 times lower. On the other hand, the minimum Ce, La, Nd
185 and Pr levels are 2, 3, 5, 26 times higher whereas our Y levels are 0.2 times lower than those Earth´s
186 crust levels.

187 Correlations among chemical elements

188 Considering all the sampling sites together, the order of abundance of chemical elements in surface
189 sediments of Chilean rivers are as follows: Ba > Nd > Pr > La > Ce > Zr > Rb > Y > Th > Nb. This
190 pattern differed a little from the enrichment factor reported in rivers from the northern hemisphere,
191 which was observed to be Ba > Zr > Ce > La > Nd > Y > Pr > Th [22].
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192 7

193 The Spearman correlation analysis (Table 5) showed some significant positive correlations
194 between Nb-Rb, Y-Zr and Ba-Zr, suggesting these metals have a common source or are redistributed
195 in the surface sediments following the same processes, as noted by some researchers [23, 29]. On the
196 other hand, negative correlations were observed between La-Th, Ce-Th, Nd-Th, Rb-Y and Ba-Y.
197 With the exception of Marchant River, the contents of the rare earth elements studied here in the
198 river sediments are very dissimilar, with coefficient of variation values (CVs) > 10% (Figure 2),
199 reflecting large heterogeneity in element contents. Our results differ from those reported by
200 researchers in sediments of Chinese and Korean rivers [27], who found high uniformity in Ce, La, Nd,
201 Pr and Y contents. The differences of geographical, mineralogical, chemical, hydrological and
202 climatic conditions over more than 4,000 km of the Chilean territory, as well as particular nearby
203 anthropogenic sources throughout the basins, could explain why the chemical element contents
204 studied here in the river sediments are very dissimilar.

205 Conclusions
206 The study of chemical elements in river sediments is important for understanding the process of
207 pollution and transport of particles occurring in a watershed. This is the first report of Ba, Ce, La, Nb,
208 Nd, Pr, Rb, Th, Y and Zr in the river sediments along Chile. The chemical element concentrations in
209 river sediments indicate different fates and destinations of these elements among Chilean rivers. The
210 river sediments showed that chemical elements remain either bound or adsorbed to carrier phases even
211 at superficial depths (under 20 cm), which means they are available for eventual remobilization to the
212 water column. From a health point of view, this is an issue particularly important in northern and
213 central Chile, where water of rivers is usually extracted for human consumption and irrigation
214 purposes. Considering the rapid development of emerging technologies, systematic studies of
215 chemical elements some of which are the focus of this paper could be helpful in assessing the
216 ecological status of catchments and related river sediments. Future studies should consider the analysis
217 of deeper sediment cores along with radioisotope dating techniques, which are required to add data
218 about the processes and sources involved in the cycling of chemical elements in the basins studied
219 here.

220 Conflicts of interest

221 The authors declare that they have no either financial or personal conflicts of interest that could
222 have influenced this paper.
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223 8

224 Acknowledgments
225 This study was financially supported by the Agencia Nacional de Investigación y Desarrollo
226 (ANID) through postdoc project FONDECYT 3200302 (W. Espejo), FONDECYT Initiation
227 11180914 (P. Bahamonde) and Millennium Science Initiative NCN16_034 and NCN2021_056.
228 Thanks to Diane Haughney for reviewing the English of the manuscript.

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256 10. MINISTERIO DEL MEDIO AMBIENTE. Quinto Informe Nacional de Biodiversidad de Chile
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314 11

315 Table 1. Mean concentrations ± SD of chemical elements in sediments of rivers form northern Chile.
316 Maximum and minimum values in parentheses (µg/g, d.w.).

317 Elements Loa River Turbio River Elqui River Choapa River

318 Ba 543.8 ± 22.41 591.7 ± 55.54 498.12 ± 37.48 433.58± 55.34

319 (556.99 - 517.95) (654.73 - 549.92) (533.08 - 458.53) (469.9 - 369.88)
320 Ce 249.53 ± 33.32 195.71 ± 53.13 188.18 ± 33.60 203.21 ± 28.20
321 (274.37 - 211.66) (255.31 - 153.32) (222.65 - 155.52) (231.4 - 175.01)
322 La 251.63 ± 10.09 210.1 ± 20.52 169.26 ± 15.39 178.8 ± 10.8
323 (261.41 - 241.25) (233.02 - 193.46) (183.72 - 170.98) (185.23 - 167.19)
324 Nb 3.75 ± 0.28 6.25 ±2.05 5.75 ± 1.14 4.53 ± 0.95
325 (4.02 - 3.47) (8.59 - 4.8) (6.89 - 4.61) (5.55 - 3.67)
326 Nd 453.2 ± 78.8 293.4 ± 43.75 265.36 ± 36.17 252.69 ± 36.48
327 (544.2 - 406.83) (333.38 - 246.68) (304.45 - 233.07) (289.49 - 216.54)
328 Pr 422.40 ± 83.5 360.96 ± 83.42 314.99 ± 27.88 343.9 ± 34.3
329 (488.89 - 328.72) (440.83 - 274.39) (346.28 - 292.78) (368.84 - 304.78)
330 Rb 30.03 ± 9.19 48.39 ± 1.81 45.57 ± 2.90 30.31 ± 2.79
331 (38.87 - 20.53) (50.25 - 46.64) (48.71 – 43.0) (32.37 - 27.14)
332 Th 10.61 ± 0.11 10.15 ± 2.52 10.49 ± 0.23 9.26 ± 0.21
333 (10.71 - 10.5) (11.92 - 7.27) (10.71 - 10.25) (9.47 - 9.06)
334 Y 9.29 ± 2.29 15.32 ± 0.69 18.07 ± 2.87 17.60 ± 7.98
335 (11.62 - 7.04) (15.72 - 14.52) (20.51 - 14.91) (19.63 - 16.34)
336 Zr 77.06 ± 9.33 134.83 ± 5.01 77.72 ± 16.11 124.54 ± 7.98
337 (87.17 - 68.78) (139.0 - 129.27) (96.17 - 66.45) (130.25 - 115.42)
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338 12

339 Table 2. Mean concentrations ± SD of chemical elements in sediments of rivers from central Chile.
340 Maximum and minimum values in parentheses (µg/g, d.w.).

341 Elements Maipo River Trancura River Correntoso River

342 Ba 275.62 ± 24.98 225.0 ± 26.08 265.35 ± 12.77

343 (293.66 - 247.11) (254.39 - 204.62) (279.4 - 254.44)
344 Ce Bdl 194.57 ± 32.90 242.60 ± 55.59
345 (231.49 - 168.34) (302.28 - 192.29)
346 La Bdl 213.02 ± 18.61 230.93 ± 33.30
347 (227.74 - 192.11) (269.37 - 210.86)
348 Nb 4.81 ± 0.86 3.07 ± 0.56 Bdl
349 (5.74 - 4.04) (3.71 - 2.69)
350 Nd Bdl 352.02 ± 65.40 414.26 ± 13.56
351 (414.84 - 284.31) (426.98 – 400.0)
352 Pr Bdl 397.50 ± 31.52 360.80 ± 44.35
353 (421.8 - 361.88) (410.22 - 324.46)
354 Rb 28.02 ± 1.43 8.53 ± 0.60 8.00 ± 0.61
355 (29.08 - 26.4) (9.0 - 7.85) (8.62 - 7.4)
356 Th 12.70 ± 1.69 8.26 ± 0.65 8.44 ± 0.65
357 (14.37 - 10.99) (8.99 - 7.75) (9.16 - 7.88)
358 Y 18.47 ± 2.19 20.94 ± 0.94 18.65 ± 0.82
359 (20.99 - 17.1) (21.57 - 19.86) (19.17 - 17.71)
360 Zr 128.96 ± 3.15 86.53 ± 4.19 73.43 ± 3.77
361 (131.79 - 125.57) (91.11 - 82.88) (77.35 - 69.82)
362 Bdl: below detection limit.
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363 13

364 Table 3. Mean concentrations ± SD of chemical elements in sediments of rivers from southern Chile.
365 Maximum and minimum values in parentheses (µg/g, d.w.).

366 Elements Marchant River Bronce River Ukika River Robalo River

367 Ba 434.84 ± 20.15 331.83 ± 22.83 231.95 ± 68.37 Bdl

368 (457.59 - 419.22) (356.79 - 311.99) (278.33 - 153.43)
369 Ce 233.03± 37.84 152.71 ± 42.30 Bdl Bdl
370 (276.29 - 206.06) (197.79 - 113.89)
371 La 220.25 ± 6.64 159.40 ± 45.34 Bdl Bdl
372 (226.73 - 213.47) (207.49 - 117.41)
373 Nb 8.52 ± 0.35 3.36 ± 0.47 3.85 ± 0.63 7.74 ± 0.80
374 (8.87 - 8.17) (3.84 - 2.91) (4.47 - 3.22) (8.3 - 6.83)
375 Nd 440.85 ± 14.55 259.25 ± 8.05 Bdl Bdl
376 (451.15 - 263.67) (267.74 - 250.75)
377 Pr 432.95 ± 10.45 270.61 ± 41.85 Bdl Bdl
378 (444.08 - 423.33) (317.95 - 238.51)
379 Rb 18.98 ± 1.41 22.17 ± 0.86 21.12 ± 0.22 18.76 ± 2.96
380 (20.58 - 17.87) (23.16 - 21.61) (21.35 - 20.91) (22.1 - 16.44)
381 Th 12.32 ± 0.20 7.19 ± 0.79 7.88 ± 2.38 16.68 ± 3.05
382 (12.52 - 12.12) (8.1 - 6.69) (10.25 - 5.5) (20.07 - 14.16)
383 Y 24.81 ± 1.68 17.28 ± 1.29 16.35 ± 1.23 18.76 ± 2.96
384 (26.66 - 23.37) (18.32 - 15.83) (17.5 - 15.05) (22.32 - 17.15)
385 Zr 163.0 ± 18.5 80.57 ± 1.55 80.06 ± 3.12 75.17 ± 8.30
386 (182.71 - 145.99) (82.31 - 79.33) (83.03 - 76.8) (82.82 - 66.34)
387 Bdl: below detection limit.
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388 14

389 Table 4. Maximum and minimum levels of chemical elements in sediments of different rivers
390 worldwide.

391 Location Chemical elements Levels (µg/g) Reference

392 Chile (several locations) Ba 654.73 - 153.43 Own study
393 Ce 302.28 - 113.89
394 La 269.37 - 117.41
395 Nb 8.87 - 2.69
396 Nd 544.2 - 216.54
397 Pr 488.89 - 238.51
398 Rb 50.25 - 7.4
399 Th 20.07 - 5.5
400 Y 26.66 - 7.04
401 Zr 182.71 - 66.34

402 Punta Arenas (southern Chile) Ba 408 - 323 [24]

403 Rb 42.6 - 32.4
404 Northern Chile (Loa River) Ba 290 – 60 [25]

England (Europe) Ce 924.4 - 59.0 [26]

La 382.4 - 28.8
405 Nd 408.2 - 26.1
Pr 111.54 - 6.84
Y 540.4 - 24.7
406 Korea (Asia) Ce 113.34 - 80.0 [27]
407 La 57.35 - 40.66
408 Nd 49.23 - 36.22
409 Pr 12.22 - 8.71
410 Y 33.02 - 24.92
411 China (Asia) Ce 92.63 - 45.98 [27]
La 45.79 - 23.1
412 Nd 42.49 - 22.12
413 Pr 10.07 - 5.12
414 Y 39.05 - 18.66

415 Mongolia (Asia) Ce 12.7 - 3.94 [20]

La 5.12 - 1.4
416 Nd 5.63 - 1.58
417 Pr 1.44 - 0.43
418 Y 2.47 - 0.92

419 Tajikistan (Central Asia) Ba 770 - 370 [23]

Ce 152 - 20
420 La 80 - 10
421 Nd 45 - 9
422 Rb 183 - 51
423 Zr 415 - 95

424 Brazil (South America) Ba 450 - 275 [11]

Nb 18.9 - 7.8
425 Rb 142.7 - 53.2
426 Th 17.7 - 7.1
427 Y 34.9 - 16.0
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428 15

429 Fig. 1. Geographical locations of the rivers studied along Chile (A: northern area; B: central area; C: southern area).
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430 16

431 Table 5. Spearman correlation coefficients among the elements studied (* ≤ 0.05).

432 La Ce Pr Nd Nb Rb Y Zr Ba

433 Ce 0.72 1

434 Pr 0.84 0.80 1

435 Nd 0.84 0.86 0.80 1

436 Nb -0.26 -0.21 -0.14 -0.28 1

437 Rb -0.15 -0.07 -0.03 -0.26 0.39* 1

438 Y -0.02 -0.07 0.06 0.08 0.13 -0.49* 1

439 Zr 0.07 -0.01 0.24 -0.01 0.39 0.26 0.27* 1

440 Ba 0.47 0.49 0.48 0.39* 0.20 0.68* -0.45* 0.28* 1

441 Th -0.13* -0.22* -0.10 -0.20* 0.69 0.16 0.18 0.22 0.03
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442 17

443 Fig. 2. Values of the coefficient of variation (CV) of rare earth element contents in Chilean river sediments (CV=standard deviation/mean value×100).
 Index

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