Abstract
The degree of toxic metal and metalloid [metal(loid)] pollution in a tributary creek, which flows along a small-scale gold mining area, was assessed using modeled speciation profile and various environmental pollution indicators. Sediment and water samples were collected from five different locations representing the creek’s upstream, midstream, and downstream areas. Concentration of As, Cd, Cu, and Pb in the sediment and aqueous samples were determined. Chemical speciation of the target analytes in the creek system was performed using geochemical software PHREEQC utilizing elemental concentration in sediment and aqueous phase, temperature, pH, dissolved oxygen, and identified minerals as input values. The concentrations of the metal(loids) in the sediments of midstream and downstream were higher compared to the average shale value (ASV) and toxicological reference values (TRV). Similarly, the total concentrations of As and Cu in creek water exceeded the local guidelines for effluent waters. Speciation results identified HAsO42−, Cd2+, CuOH+, and PbOH+ as the major species of the target analytes. Supersaturation of elements in sediment and low solubility in the aqueous matrix point out to resuspension and transport of metals as colloidal suspensions. The enrichment factor (EF) and geoaccumulation index (Igeo) values indicate significant levels of enrichment and pollution in the midstream and downstream areas. The increasing pollution load index (PLI) suggested the progressive deterioration from the upstream (0.8 to 1.7) down toward the midstream (PLI = 2.0 to 18.0) and downstream (PLI = 2.4 to 17.5). Speciation and environmental index results confirmed that anthropogenic sources in the midstream were transported to the downstream catchment.
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References
Abrahim GMS, Parker RJ (2008) Assessment of heavy metal enrichment factors and the degree of contamination in marine sediments from Tamaki Estuary, Auckland, New Zealand. Environ Monitor Assess 136(1):227–238. https://doi.org/10.1007/s10661-007-9678-2
Aleksander-Kwaterczak U, Plenzler D (2019) Contamination of small urban watercourses on the example of a stream in Krakow (Poland). Environ Earth Sci 78(16):1–13. https://doi.org/10.1007/s12665-019-8509-4
Aleksander-Kwaterczak U, Kostka A, Leśniak A (2021) Multiparameter assessment of select metal distribution in lacustrine sediments. J Soils Sediments 21(1):512–529. https://doi.org/10.1007/s11368-020-02732-x
Alexakis D (2016) Human health risk assessment associated with Co, Cr, Mn, Ni and V contents in agricultural soils from a Mediterranean site. Arch Agron Soil Sci 62(3):359–373. https://doi.org/10.1080/03650340.2015.1062088
Alexakis DE (2021) Multielement contamination of land in the margin of highways. Land 10(3):230. https://doi.org/10.3390/land10030230
Alexakis DE, Bathrellos GD, Skilodimou HD, Gamvroula DE (2021) Spatial distribution and evaluation of arsenic and zinc content in the soil of a karst landscape. Sustainability 13(12):6976. https://doi.org/10.3390/su13126976
Alkan N, Alkan A, Akbaş U, Fisher A (2015) Metal pollution assessment in sediments of the southeastern black sea coast of Turkey. Soil Sediment Contam Int J Soils Sediments 24(3):290–305. https://doi.org/10.1080/15320383.2015.950723
Alkan N, Alkan A, Demirak A, Bahloul M (2020) Metals/metalloid in marine sediments, bioaccumulating in macroalgae and a mussel. Soil Sediment Contam Int J 29(5):569–594. https://doi.org/10.1080/15320383.2020.1751061
Alkan A, Alkan N, Aktaş M (2021) Comparison of Ni enrichment and background concentrations in the Southeastern Black Sea sediments. Environmental Forensics 22(3–4):364–371. https://doi.org/10.1080/15275922.2020.1850559
Alloway BJ (2013) Sources of heavy metals and metalloids in soils. In: Springer (ed) Heavy metals in soils. Springer, Dordrecht, pp 11–50
Austria ES, Nuesca GM, Lamorena RB (2018) Spectral fitting approach for the determination of enrichment and contamination factors in mining sediments using laser-induced breakdown spectroscopy. Environ Sci Pollut Res 25(17):16620–16628. https://doi.org/10.1007/s11356-018-1803-y
Barangay Profiles 2019—Itogon (2019). http://itogon.gov.ph/images/2020/pdf/barangay/Tinongdan.pdf
Brady JP, Ayoko GA, Martens WN, Goonetilleke A (2014) Temporal trends and bioavailability assessment of heavy metals in the sediments of Deception Bay, Queensland, Australia. Mar Pollut Bull 89(1–2):464–472. https://doi.org/10.1016/j.marpolbul.2014.09.030
Brümmer GW, Barrow NJ, Fischer L (2013) Effect of porosity of goethite on the sorption of six heavy metal ions. Eur J Soil Sci 64(6):805–813
Burnol A (2006) Eléments traces métalliques. INERIS, Verneuil-en-Halatte
Capangpangan RY, Cane ALF, Lincuna ME, Rañon JA, Obena RAP, Pineda CP (2016) Speciation and bioavailability of trace metals (Cd, Cu and Pb) in marine sediment samples from placer Bay near Manila Mining Corporation, Surigao City, Philippines. Annals Stud Sci Humanit 1:12–34
Cerozi BdS, Fitzsimmons K (2016) The effect of pH on phosphorus availability and speciation in an aquaponics nutrient solution. Bioresour Technol 219:778–781. https://doi.org/10.1016/j.biortech.2016.08.079
Clemente E, Sera K, Futatsugawa S, Murao S (2004) PIXE analysis of hair samples from artisanal mining communities in the Acupan region, Benguet, Philippines. Nucl Instrum Methods Phys Res Sect B 219–220:161–165. https://doi.org/10.1016/j.nimb.2004.01.046
Cooke DR, Deyell CL, Waters PJ, Gonzales RI, Zaw K (2011) Evidence for magmatic-hydrothermal fluids and ore-forming processes in epithermal and porphyry deposits of the Baguio District, Philippines. Econ Geol 106(8):1399–1424. https://doi.org/10.2113/econgeo.106.8.1399
Corpus TJ, Maglambayan CPDSMV (2011) Small-scale Gold Mining in the Ambalanga Catchment, Philippines: its Control on Mercury Methylation in Stream Sediments. Int J Environ Sci 2(2):1048–1059
David CP (2002) Heavy metal concentrations in marine sediments impacted by a mine-tailings spill, Marinduque Island, Philippines. Environ Geol 42(8):955–965. https://doi.org/10.1007/s00254-002-0601-4
Duzgoren-Aydin NS, Wong CSC, Song ZG, Aydin A, Li XD, You M (2006) Fate of heavy metal contaminants in road dusts and gully sediments in Guangzhou, SE China: a chemical and mineralogical assessment. Hum Ecol Risk Assess Int J 12(2):374–389. https://doi.org/10.1080/10807030500538005
Espiritu EQ, Claveria RJR, Bernadas PJC (2022) Assessment of surface water quality and mercury levels from Artisanal and small-scale gold mining (ASGM) along Acupan River, Benguet, Philippines. Environ Geochem Health 44:3655–3676. https://doi.org/10.1007/s10653-021-01137-0
Fairgray ME, Webster-Brown JG, Pope J (2020) Testing geochemical predictions of trace element toxicity and bioavailability at a rehabilitated mine site. Mine Water Environ 39(1):75–92. https://doi.org/10.1007/s10230-019-00644-y
Förstner U, Wittmann GTW (2012) Metal pollution in the aquatic environment. Springer Science & Business Media, New York
Garwin S, Hall R, Watanabe Y (2005) Tectonic setting, geology, and gold and copper mineralization in cenozoic magmatic arcs of Southeast Asia and the West Pacific. In
Goher ME, Farhat HI, Abdo MH, Salem SG (2014) Metal pollution assessment in the surface sediment of Lake Nasser, Egypt. Egypt J Aquat Res 40(3):213–224. https://doi.org/10.1016/j.ejar.2014.09.004
Gu Y, Lin Q, Yu Z, Wang X, Ke C, Ning J (2015) Speciation and risk of heavy metals in sediments and human health implications of heavy metals in edible nekton in Beibu Gulf, China: a case study of Qinzhou Bay. Mar Pollut Bull 101(2):852–859. https://doi.org/10.1016/j.marpolbul.2015.11.019
Herbert RB (1996) Metal retention by iron oxide precipitation from acidic ground water in Dalarna, Sweden. Appl Geochem 11(1–2):229–235
Imai A (2002) Metallogenesis of porphyry Cu deposits of the Western Luzon Arc, Philippines: K-Ar ages, SO3 contents of microphenocrystic apatite and significance of intrusive rocks. Resour Geol 52(2):147–161. https://doi.org/10.1111/j.1751-3928.2002.tb00127.x
Islam MS, Ahmed MK, Raknuzzaman M, Mamun MH-A, Islam MK (2015) Heavy metal pollution in surface water and sediment: a preliminary assessment of an urban river in a develo** country. Ecol Ind 48:282–291. https://doi.org/10.1016/j.ecolind.2014.08.016
Itogon Annual Weather Averages (2023). https://www.worldweatheronline.com/itogon-weather-averages/benguet/ph.aspx. Accessed 2 Jan 2023
Li X, Liu L, Wang Y, Luo G, Chen X, Yang X, Gao B, He X (2012) Integrated assessment of heavy metal contamination in sediments from a coastal industrial basin NE China. PLoS ONE 7(6):e39690. https://doi.org/10.1371/journal.pone.0039690
Lis J, Pasieczna A (1995) Geochemical Atlas of Poland on a scale 1:2500000. from Państwowy Instytut Geologiczny, Warszawa
Loring DH (1991) Normalization of heavy-metal data from estuarine and coastal sediments. ICES J Mar Sci 48(1):101–115
Magu MM, Govender PP, Ngila JC (2016) Geochemical modelling and speciation studies of metal pollutants present in selected water systems in South Africa. Phys Chem Earth Parts a/b/c 92:44–51. https://doi.org/10.1016/j.pce.2015.08.001
Manta DS, Angelone M, Bellanca A, Neri R, Sprovieri M (2002) Heavy metals in urban soils: a case study from the city of Palermo (Sicily), Italy. Sci Total Environ 300(1–3):229–243. https://doi.org/10.1016/S0048-9697(02)00273-5
Martin J, Whitfield M (1983) The significance of the river input of chemical elements to the ocean. Trace metals in sea water. Springer, Boston, pp 265–296
Meng D, Li J, Liu T, Liu Y, Yan M, Hu J, Li X, Liu X, Liang Y, Liu H, Yin H (2019) Effects of redox potential on soil cadmium solubility: Insight into microbial community. J Environ Sci 75:224–232. https://doi.org/10.1016/j.jes.2018.03.032
Mindat.org. (2023). https://www.mindat.org/feature-1732265.html. Accessed 2 Jan 2023
Miranda LS, Wijesiri B, Ayoko GA, Egodawatta P, Goonetilleke A (2021) Water-sediment interactions and mobility of heavy metals in aquatic environments. Water Res 202:117386. https://doi.org/10.1016/j.watres.2021.117386
Müller G (1969) Index of geoaccumulation in sediments of the Rhine River. GeoJournal 2:108–118
Müller G (1981) Die schwermetallbelstung der sedimente des neckars und seiner nebenflusse: eine estandsaufnahme. Chem Zeitung 105:157–164
Nasrabadi T, Soodarjani AE, Karbassi A, Baghdadi M (2022) Role of salinity and aeration on flocculation and remobilization of metals during estuarine mixing. Environ Earth Sci 81(10):1–8. https://doi.org/10.1007/s12665-022-10413-w
PAGASA (2023) Climate projections. https://bagong.pagasa.dost.gov.ph/climate/climate-change/dynamic-downscaling/climap. Accessed 2 Jan 2023
Parkhurst DL, Appelo CAJ (2013) Description of input and examples for PHREEQC version 3: a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. US geological survey techniques and methods 6(A43), 497. R https://pubs.usgs.gov/tm/06/a43/
Qi C, Xu X, Chen Q, Liu H, Min X, Fourie A, Chai L (2022) Ab initio calculation of the adsorption of As, Cd, Cr, and Hg heavy metal atoms onto the illite(001) surface: Implications for soil pollution and reclamation. Environ Pollut 312:120072. https://doi.org/10.1016/j.envpol.2022.120072
Reddy KJ, Wang L, Gloss SP (1995) Solubility and mobility of copper, zinc and lead in acidic environments. Plant Soil 171:53–58. https://doi.org/10.1007/BF00009564
Sharma VK, Sohn M (2009) Aquatic arsenic: toxicity, speciation, transformations, and remediation. Environ Int 35(4):743–759. https://doi.org/10.1016/j.envint.2009.01.005
Shikazono N, Tatewaki K, Mohiuddin KM, Nakano T, Zakir HM (2012) Sources, spatial variation, and speciation of heavy metals in sediments of the Tamagawa River in Central Japan. Environ Geochem Health 34(1):13–26. https://doi.org/10.1007/s10653-011-9409-z
Sinex SA, Helz GR (1981) Regional geochemistry of trace elements in Chesapeake bay sediments. Environ Geol 3(6):315–323
Song B, Zeng G, Gong J, Liang J, Xu P, Liu Z, Zhang Y, Zhang C, Cheng M, Liu Y, Ye S, Yi H, Ren X (2017) Evaluation methods for assessing effectiveness of in situ remediation of soil and sediment contaminated with organic pollutants and heavy metals. Environ Int 105:43–55. https://doi.org/10.1016/j.envint.2017.05.001
Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Anal Chem 51(7):844–851
Thorslund J, Jarsjö J, Wällstedt T, Mörth CM, Lychagin MY, Chalov SR (2017) Speciation and hydrological transport of metals in non-acidic river systems of the Lake Baikal basin: field data and model predictions. Reg Environ Change 17(7):2007–2021. https://doi.org/10.1007/s10113-016-0982-7
Tomlinson DL, Wilson JG, Harris CR, Jeffrey DW (1980) Problems in the assessment of heavy-metal levels in estuaries and the formation of a pollution index. Helgoländer Meeresuntersuchungen 33(1):566–575. https://doi.org/10.1007/BF02414780
Turekian KK, Wedepohl KH (1961) Distribution of the elements in some major units of the Earth’s crust. Geol Soc Am Bull 72(2):175–192. https://doi.org/10.1130/0016-7606(1961)72[175:DOTEIS]2.0.CO;2
USEPA (1999) Screening level ecological risk assessment protocol for hazardous waste combustion facilities, vol. 3, Appendix E: Toxicity reference values. (EPA 530-D99-001C)
Verbrugge B (2017) Small-scale gold mining and the state in the Philippines. In: Extractivism C (ed) Society and the state. Palgrave Macmillan, London, pp 101–125
Wang C, Liu S, Zhao Q, Deng L, Dong S (2012) Spatial variation and contamination assessment of heavy metals in sediments in the Manwan Reservoir, Lancang River. Ecotoxicol Environ Saf 82:32–39. https://doi.org/10.1016/j.ecoenv.2012.05.006
Water Quality Guidelines and General Effluent Standards of 2016, Administrative Order No. 08 Series of 2016 C.F.R. (2016).
Windisch J, Gradwohl A, Gilbert BM, Santos QMD, Wallner G, Avenant-Oldewage A, Jirsa F (2022) Toxic elements in sediment and water of the Crocodile river (West) System, South Africa, following acid mine drainage. Appl Sci 12(20):10531. https://doi.org/10.3390/app122010531
Zhang J, Liu CL (2002) Riverine composition and estuarine geochemistry of particulate metals in China—weathering features, anthropogenic impact and chemical fluxes. Estuar Coast Shelf Sci 54(6):1051–1070. https://doi.org/10.1006/ecss.2001.0879
Zhang C, Yu Z, Zeng G, Jiang M, Yang Z, Cui F, Zhu M, Shen L, Hu L (2014) Effects of sediment geochemical properties on heavy metal bioavailability. Environ Int 73:270–281. https://doi.org/10.1016/j.envint.2014.08.010
Zhao Y, Marriott SB (2013) Dispersion and remobilisation of heavy metals in the River Severn system, UK. Proc Environ Sci 18:167–173. https://doi.org/10.1016/j.proenv.2013.04.022
Acknowledgements
The authors would also like to thank the research groups of Dr. Lilibeth dlc. Coo and Dr. Emilyn Q. Espiritu, who also worked under the CSMP (CSMSMP), for providing support in the sampling and data collection of creek samples.
Funding
This research study was funded by the Department of Science and Technology—Philippine Council for Industry, Energy and Emerging Technology Research Development (DOST-PCIEERD) under the Chemical Sensors for Mine Site Monitoring Program (CSMSMP).
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ESAJr.: methodology, formal analysis, validation, investigation, data curation, and writing—original draft. EMF: methodology, formal analysis, validation, and investigation. RBL: supervision, project administration, funding acquisition, conceptualization, review, and editing.
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Austria, E.S., Fuentes, E.M. & Lamorena, R.B. Metal and metalloid speciation and pollution assessment across a small-scale mining creek system tributary. Environ Earth Sci 82, 217 (2023). https://doi.org/10.1007/s12665-023-10918-y
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DOI: https://doi.org/10.1007/s12665-023-10918-y