Predicting bioavailability of potentially toxic elements (PTEs) in sediment using various machine learning (ML) models: A case study in Mahabad Dam and River-Iran.

Considering the significant impact of potentially toxic elements (PTEs) on the ecosystem and human health, this paper, investigated the contamination level of four PTEs (Zn, Cu, Mo and Pb) and their mobility in sediments of Mahabad dam and river. Choosing the most effective machine learning algorithms is very important in accurately predicting bioavailability of PTEs. Therefore, four machine learning (ML) models including decision tree regression (DTR), random forest regression (RFR), multi-layer perceptron regression (MLPR) and support vector regression (SVR), were used and compared for estimating the selected PTEs bioavailability. For these models, 9 variables (total concentration, pH, EC, OM and five chemical forms F1 to F5 obtained by sequential extraction) in 100 sediment samples were considered. The results showed that contamination level decreases from Zn and Cu to Pb and Mo, but the order of the mobility coefficient of the elements in the sediment follows the trend of zinc > copper > molybdenum > lead, and variation coefficient indicated more variability of spatial distribution for Zn and Cu. Among the four tested models, DTR and RFR performed the best for predicting PTEs bioavailability variations (with roc_auc>0.9, R2 > 0.8 and MSE>0.5), followed by MLPR and SVR. Furthermore, the relevance of the factors controlling the metals availability, evaluated using the RFR-based feature importance method and Pearson correlation, revealed that the most important physicochemical property for Zn, Cu and Mo bioavailability was pH, whereas for Pb, EC was the determinant factor. In the case of chemical speciation, F5 had an inverse correlation with the target, while F1 and F2 had a direct correlation. These fractions contributed significantly to the prediction results. This study represents the potential successful application of ML to PTEs risk control in sediments and early warning for the surrounding water PTEs contamination.

Polycyclic aromatic hydrocarbons (PAHs) in soils around oil refineries; Case study: Erbil and Kirkuk refineries, Iraq- A modelling approach.

Purpose: Political tensions in Iraq have made attention to environmental issues not a priority for the authorities. Therefore, the influence of Kirkuk and Erbil refineries on contamination of the surrounding soil by polycyclic aromatic hydrocarbons (PAHs), were studied. Methods: 25 soil samples were collected and analyzed using high-performance liquid chromatography (HPLC), and their fate and health risk were investigated using Exposure Model for Soil-Organic Fate and Transport (EMSOFT) and the Monte Carlo Simulation (MCS) model. Results: High ∑PAHs contamination (raged from 212.8 to 12,790.4 ppb), the dominance of pyrogenic sources, and high ecological risk were observed. The mean hazard index values for children (0.043) are higher than those for adults (0.02), while the incremental lifetime carcinogenic risk values for adults (8.50E-4) are greater than those for children (5.27E-4). Pyrene is the significant soil PAH from the depth of 3 cm downwards, while phenanthrene and fluorene are the major constituents of PAHs between the depth of 3 and 10 cm. Also, low molecular weight PAHs significantly decrease in soil layers over the time frame, and maximum PAHs concentrations belong to high molecular weight PAHs over 20 years. Conclusion: Using an appropriate monitoring system, as well as sound management decisions to reduce the emission of environmental pollution are needed. Also, it seems that the use of constant values for soil physicochemical parameters such as moisture and porosity, despite seasonal variations, may result in uncertainty for fate and transport modelling. Therefore, seasonal sampling and analysis of soil parameters, would be helpful. Supplementary Information: The online version contains supplementary material available at 10.1007/s40201-022-00809-y.

Bioavailability, distribution and health risk assessment of arsenic and heavy metals (HMs) in agricultural soils of Kermanshah Province, west of Iran.

Kermanshah Province as an agricultural hub exports food crops to neighboring countries. In this study, contamination status, bioavailability, spatial distribution, and ecological and human health risk of arsenic and heavy metals (HMs) in soil were investigate. For this purpose, 121 agricultural soil samples were collected and analyzed using ICP-MS. The data were studied by calculating some geochemical indices, and using geographical information system and statistical analysis. Results showed that Cd has the highest bioavailability, following by Cu and As. Also, Cu was severely associated with organic matter. Enrichment factor (EF) followed the order of As > Cu > Pb > Se > Cd > Zn > Ni > Cr, and the soil pollution index (SPI) ranged from 0.82 to 2.65. Low potential ecological risk was measured for most of the samples. However, Kermanshah County and Eastern parts of the Province showed the highest HMs enrichment and ecological risk. Moreover, high carcinogenic risk of Cr and Ni threatens the children. Cr showed also high non-carcinogenic hazard index (HI) for children. Principal component analysis (PCA) indicated the anthropogenic origins for As, Cd, Cu, Pb, Se and Zn, while Cr and Ni originated mainly from a geogenic source. Furthermore, Kruskal-Wallis H test revealed that As, Cd, Cr, Cu, Ni, Pb, Se and Zn concentrations were significantly different (p < 0.05) between 16 Counties of the Kermanshah Province. Overall, the management of urban and industrial contamination sources is required to minimize the concentration of bioavailable portion of HMs and preventing residents of the area from being exposed to contaminants.

Arsenic in the rock-soil-plant system and related health risk in a magmatic-metamorphic belt, West of Iran.

Following earlier reports of water contamination and arsenic (As) toxicity symptoms in residents of Kurdistan Province, As was determined in rock, soil and plant samples to investigate its fate from rock to crops and its potential effects on human health. Total As content ranged from 4.9 to 10,000 mg/kg, 7.7-430 mg/kg and < 0.05-25,079 µg/kg (dry weight) in rock, soil and plant samples, respectively. The Qorveh-Bijar region data indicated that magmatic differentiation has enriched late magmatic fluids in As. High rare earth elements concentration, dissociation coefficient, and positive Eu anomaly in volcanic rocks, indicated the prevalence of intermediate to felsic composition. The highest As concentration was measured in travertine. In soil, As average level in Qorveh and Bijar was 48.5 and 107 mg/kg, respectively. Higher pollution index and geoaccumulation index (Igeo) were also calculated for Bijar County. The As concentration in crop samples was greater than the recommended maximum permissible concentration for foodstuff. Mann-Whitney U test revealed significant differences between As concentration in different plant species and no difference between plants in Bijar and Qorveh. Also, alfalfa displayed the highest biological accumulation coefficient among the investigated plants. The calculated chronic daily intake of As in Bijar County was higher than the recommended levels for wheat and barley grains. Moreover, the hazard quotient (HQ) and incremental lifetime cancer risk assessments revealed high non-cancer (HQ > 1 for both adults and children) and cancer (particularly for barley in Bijar) risks for inhabitants via consumption of As contaminated crops cultivated in the study area.

Influence of natural and urban emissions on rainwater chemistry at a southwestern Iran coastal site.

The influence of pollutant sources on rainwater chemistry is investigated at an industrial coastal site in Iran (Mahshahr) where frequent dust storms occur throughout the year. For this purpose, rainwater samples from two main pluvial systems were collected and analyzed for major ions and selected heavy metals (Al, Cu, Ni, Pb and Zn). The differences in calculated and measured pH values of rainwater pointed to the important effect of neutralizing agents, specifically Ca2+, Na+ and Mg2+, in offsetting the high acidity generated by NO3- and SO42- to yield alkaline rainwater. A comparison of species concentration ratios relative to those for pure seawater and Earth's crust revealed that nearly all NO3- and most Ca2+, SO42- and Mg2+ originated from non-marine and local sources. Compared with other areas around the world, some heavy metals (particularly Zn) displayed higher concentrations in Mahshahr rainwater. Enrichment factor (EF) analysis revealed that Cu and Ni were moderately enriched, while Pb and Zn in particular (EF > 100) were highly enriched indicating that these species in rainwater stemmed from anthropogenic activities. Positive matrix factorization (PMF) modeling indicated that the four main pollutant sources impacting the regional rainwater were soil, combustion processes, marine emissions, and the local industrial sources.

Contamination, health risk, mineralogical and morphological status of street dusts- case study: Erbil metropolis, Kurdistan Region-Iraq.

Street dusts contamination by heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs), their mineralogical and morphological properties were investigated in Erbil metropolis. A total of 43 soil and street dust samples were collected and analyzed, and SPSS, ImageJ, X-powder and positive matrix factorization (PMF) software were used for data analyzing. Results showed the role of geology in mineralogical status of dusts. Based on ImageJ software processing, dust particles with diameters below 10 µm and low circularity and roundness were dominant. The enrichments for Hg, Cu, Pb and Zn contents were observed in compare with their calculated local geochemical baselines and geoaccumulation index, while, Ni, Co and Cr were categorized as particularly unpolluted. However, Hg, Cu and Pb showed the highest ecological risk (Eji) values among the studied elements, and 25.80%, 25.80% and 12.90% of the samples were classified as very high, moderate and considerable potential ecological risks, respectively. Hazard index (HI) followed the decreasing order of Pb > Cr > Cu > Ni > Hg > Zn > Co, and ingestion was the main exposure route particularly for children. The concentrations of individual PAHs ranged from 1.06 to 1000 ng/g, with the dominance of 3 and 4-ring compounds. Also, non-carcinogenic PAHs concentrations were higher than carcinogenic compounds and toxic equivalents (TEQs) ranged from 22.30 to 246.92 ng/g, with a max value in Northern industrial zone. Finally, source identification using multivariate statistics and PMF introduced three main PAHs and HMs sources in the study area including geogenic, traffic and industries, and incinerators (mainly for medical wastes).

Heavy metal contamination and health risk assessment in three commercial fish species in the Persian Gulf.

Five heavy metals/metalloids and related potential health risks were investigated in three commercially important fish species (Anodontostoma chacunda, Belangerii, and Cynoglossurs arel) in Musa Estuary and Mahshahr Harbour of the Persian Gulf. A total of 116 fish samples were collected, and their liver and muscle organs were separately analyzed using ICP-MS. Results revealed that studied metals concentrations (with some exceptions) varied among sampling stations, fish species and their organs. Human health risk is evaluated using different indices. The results indicated that arsenic and mercury are the most hazardous elements. Estimated daily intake (EDI) for the metals exceeded the provisional tolerable daily intake (PTDI) for all studied fish species. Also, target risk (TR) of arsenic indicated that consumption over a long period of time may result in a carcinogenic effect. The results are expected to create awareness among the public on the safety of consuming food products grown in particular areas.

Heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) in soils of different land uses in Erbil metropolis, Kurdistan Region, Iraq.

Urban soil contamination is a growing concern for the potential health impact on the increasing number of people living in these areas. In this study, the concentration, the distribution, the contamination levels, and the role of land use were investigated in Erbil metropolis, the capital of Iraqi Kurdistan. A total of 74 soil samples were collected, treated, and analyzed for their physicochemical properties, and for 7 heavy metals (As, Cd, Cr, Cu, Fe, Pb, and Zn) and 16 PAH contents. High concentrations, especially of Cd, Cu Pb, and Zn, were found. The Geoaccumulation index (Igeo), along with correlation coefficients and principal component analysis (PCA) showed that Cd, Cu, Pb, and Zn have similar behaviors and spatial distribution patterns. Heavy traffic density mainly contributed to the high concentrations of these metals. The total concentration of ∑PAHs ranged from 24.26 to 6129.14 ng/g with a mean of 2296.1 ng/g. The PAH pattern was dominated by 4- and 5-ring PAHs, while diagnostic ratios and PCA indicated that the main sources of PAHs were pyrogenic. The toxic equivalent (TEQ) values ranged from 3.26 to 362.84 ng/g, with higher values in central parts of the city. A statistically significant difference in As, Cd, Cu, Pb, Zn, and ∑PAH concentrations between different land uses was observed. The highest As concentrations were found in agricultural areas while roadside, commercial, and industrial areas had the highest Cd, Cu, Pb, Zn, and ∑PAH contents.

Heavy metals and polycyclic aromatic hydrocarbons in surface sediments of Karoon River, Khuzestan Province, Iran.

Karoon is the longest river in Iran and provides water for industries located along its banks, such as metal, petrochemical, and oil industries. It is also the source of drinking water for cities such as Ahwas, Abadan, and Khorramshahr. In this study, 34 and 18 surface sediment samples were collected and analyzed for heavy metals (Al, As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and polycyclic aromatic hydrocarbons (PAHs). The measured concentrations of heavy metals were compared with US EPA sediment quality guidelines, and the results showed that Cu concentration was above the threshold effect level (TEL) in 65.67% of the samples and Hg concentration was above the effect range median (ERM) in some samples. The results revealed that Hg was severely enriched (5 < enrichment factor < 20) and classified in very high ecological risk index category. It is the major metallic contaminant in the study area. The total PAH concentrations ranged from 11.54-117,730 µg/kg, with the mean value of 7034.55 µg/kg dominated by lower molecular weight (LMW) PAHs. The total potentially carcinogenic PAHs (∑cPAHs) in sediment samples ranged from 2.09 to 31,930 µg/kg, indicating high carcinogenic potential of sediments in the study area. The total toxic equivalent (TEQ) values ranged from 1.06 to 7228.7 µg/kg. Maximum TEQ occurred in Abadan oil refinery station followed by Khorramshahr soap factory and Abadan petrochemical complex. Principal component analysis and cluster analysis also revealed the relationships between the studied parameters and identified their probable sources.

Macronutrients and trace metals in soil and food crops of Isfahan Province, Iran.

The distribution of 10 macronutrients and trace metals in the arable soils of Isfahan Province, their phytoavailability, and associated health risks were investigated; 134 plant and 114 soil samples (from 114 crop fields) were collected and analyzed at harvesting time. Calculation of the soil pollution index (SPI) revealed that arable soil polluted by metals was more severe in the north and southwest of the study area. The results of cluster analysis indicated that Pb, Zn, and Cu share a similar origin from industries and traffic. The concentrations of macronutrients and trace metals in the sampled crops were found in the order of K > Ca > S > Mg > P and Fe > Mn > Zn > Cu > Pb, respectively, whereas calculation of the bioconcentration factor (BCF) indicated that the accumulation of the investigated elements in crops was generally in the order of S ≈ K > P > Mg > Ca and Zn > Cu > Mn > Pb > Fe, respectively. Thus, various parameters including crop species and the physical, chemical, and biological properties of soil also affected the bioavailability of the elements besides the total element contents in soil. Daily intake (DI) values of elements were lower than the recommended daily intake (RDI) levels in rice grains except for Fe and Mn, but for wheat grains, all elements displayed DI values higher than the RDI. Moreover, based on the hazard index (HI) values, inhabitants are experiencing a significant potential health risk solely due to the consumption of wheat and rice grains (particularly wheat grains). Mn health quotient (HQ) also indicated a high risk of Mn absorption for crop consumer inhabitants.