A comprehensive study of the chemical composition of rainwater was carried out from October 2016 to September 2017 in the equatorial tropical rainforest region of northwestern Borneo. Monthly cumulative rainwater samples were collected from different locations in the Limbang River Basin (LRB) and were later categorized into seasonal samples representing northeast monsoon (NEM), southwest monsoon (SWM), and inter-monsoon (IM) periods. Physical parameters (pH, EC, TDS, DO, and turbidity), major ions (HCO3-, Cl-, Ca2+, Mg2+, Na+, and K+) and trace metals (Co, Ni, Cd, Fe, Mn, Pb, Zn, and Cu) were analyzed from collected rainwater samples. Rainwater is slightly alkaline with mean pH higher than 5.8. Chloride and bicarbonate are the most abundant ions, and the concentration of major ions in seasonal rainwater has shown slight variation which follows a descending order of HCO3-> Cl-> Na+ > Ca2+ > Mg2+ > K+ in NEM and Cl- > HCO3- > Na+ > Ca2+ > K+ > Mg2+ in SWM and Cl- > HCO3- > Na+ > Ca2+ > Mg2+ > K+ in IM period. Trace metals such as Fe and Ni have shown dominance in seasonal rainwater samples, and all the metals have shown variation in concentration in different seasons. Variation in chemical characteristic of seasonal rainwater samples identified through piper diagram indicates dominance of Ca2+-Mg2+-HCO3- and mixed Ca2+-Mg2+-Cl- facies during NEM, SWM, and IM periods. Statistical analysis of the results through two-way ANOVA and Pearson's correlation also indicates significant variation in physico-chemical characteristics. This suggests a variation in contributing sources during the monsoon seasons. Factor analysis confirmed the source variation by explaining the total variance of 79.80%, 90.72%, and 90.52% with three factor components in NEM, SWM, and IM rainwater samples with different loading of parameters. Enrichment factor analysis revealed a combined contribution of marine and crustal sources except K+ which was solely from crustal sources. Sample analysis of backward air mass trajectory supports all these findings by explaining seasonal variation in the source of pollutants reaching the study area. Overall, the results show that the chemical composition of seasonal rainwater samples in LRB was significantly influenced by natural as well as anthropogenic processes. These include (long-range and local) industrial activities, fossil fuel combustion, forest burning, transportation activities including road transport and shipping activities, and land-derived soil dust along with chemical constituents carried by seasonal wind.
Micro-mapping of terrestrial gamma radiation dose (TGRD) at meter grid spacing in and around four urban homes in Miri City shows rates ranging from 70 to 150 nGy/h. Tiled surfaces (floors and walls) vary between properties and have a clear and significant influence on TGRD which is highest in kitchens, washrooms and toilets. Application of a single indoor value for annual effective dose (AED) may lead to underestimations of up to 30%. The AED is unlikely to exceed 0.8 mSv in homes of this type in Miri, which is within recommended guidelines.
Evaluation of the hydrogeochemical processes governing the heavy metal distribution and the associated health risk is important in managing and protecting the health of freshwater resources. This study mainly focused on the health impacts due to the heavy metals pollution in a known Cretaceous-Tertiary (K/T) contact region (Tiruchinopoly, Tamilnadu) of peninsular India, using various pollution indices, statistical, and geochemical analyses. A total of 63 samples were collected from the hard rock aquifers and sedimentary formations during southwest monsoon and analysed for heavy metals, such as Li, Be, Al, Rb, Sr, Cs, Ba, pb, Mn, Fe, Cr, Zn, Ga, Cu, As, Ni, and Co. Ba was the dominant element that ranged from 441 to 42,638 μg/l in hard rock aquifers, whereas Zn was the major element in sedimentary formations, with concentrations that ranged from 44 to 118,281 μg/l. The concentrations of Fe, Ni, Cr, Al, Cr, and Ni fell above the permissible limit in both of the formations. However, the calculated heavy metal evaluation index (HEI), heavy metal pollution index (HPI), and the degree of contamination (Cd) parameters were higher in the sedimentary formation along the contact zone of the K/T boundary. Excessive health risks from consumption of contaminated groundwater were mostly confined to populations in the northern and southwestern regions of the study area. Carcinogenic risk assessment suggests that there are elevated risks of cancer due to prolonged consumption of untreated groundwater. Ba, Sr, and Zn were found to be geochemically highly mobile due to the partitioning between the rock matrix and groundwater, aided by the formation of soluble carbonato-complexes. Factor analysis indicates that the metals are mainly derived from the host rocks and anthropogenic inputs are relatively insignificant. Overall, this study indicated that groundwater in K/T contact zones is vulnerable to contamination because of the favorable geochemical factors. Long-term monitoring of such contact zones is required to avert the potential health hazards associated with consumption of the contaminated groundwater.
Hydrogeochemical understanding of groundwater is essential for the effective management of groundwater. This study has been carried out to have concrete data for the seasonal variations in hydrogeochemistry of groundwater in central Tamilnadu forming a complex geological terrain with a varied lithology. A total of 244 groundwater samples were collected during four different seasons, viz, southwest monsoon (SWM), summer (SUM), postmonsoon (POM), and northeast monsoon (NEM) from bore wells. The physical parameters such as pH, temperature, TDS, ORP, humidity, and electrical conductivity (EC) were measured insitu, whereas major ions were analyzed in the lab adopting standard procedures. Overall, higher EC and NO3 values were observed and exceeded the WHO permissible limit irrespective of seasons, except for NO3 in SWM. Na and HCO3 are the dominant cation and anion in the groundwater irrespective of seasons. The highest average values of Na (65.06 mg L-1) and HCO3 (350.75 mg L-1) were noted during SWM. Statistical analysis was carried out to elucidate the hydrogeochemistry of the region. Initially, to understand the ionic relationship, correlation matrix was used followed by factor analysis for determination of major geochemical control and later factor scores were derived to understand the regional representations. An attempt has also been made to identify the samples influenced by multiple geochemical processes and to understand their spatial variation in the study period. Correlation of geochemical parameters reveals a excellent positive correlation between Ca and NO3 in SUM, SWM, and NEM due to the dominant of anthropogenic sources and minor influence of weathering process. Strongly loaded factor scores are found to be mostly in the following order POM > NEM > SWM > SUM. Principal component analysis of different seasons indicates the interplay of natural weathering and anthropogenic factors. Overall, the predominant geochemical processes in this region, irrespective of seasons are weathering and, ion exchange and anthropogenic activities.
This study considered the temporal variations in rainfall and water level patterns as governing factors, which influence the geochemical process of coastal aquifer around Pondicherry, South India. Rainfall and water level data were collected from 2006 to 2016, which showed that the amount of rainfall from 2006 to 2011 was higher than that of 2011 to 2016. To understand the geochemical process governing groundwater, samples were collected during 2006 (n = 54), followed by 2011 (n = 93), and during 2016 (n = 63) as part of continuous observation. The major ions and stable isotopes (δ18O and δD) were analyzed in the samples to determine the geochemical variations. The predominant types were noted as Na-HCO3 and Na-Cl; Ca-HCO3 and Ca-Mg-Cl; and Na-Cl and Ca-Mg-Cl in 2006, 2011, and 2016, respectively. Saturation states of sulfate and carbonate minerals were compared for the study periods and it indicates that the saturation index (SI) values were increased from 2006 to 2011, but decreased from 2011 to 2016. PHREEQC inverse modeling revealed the predominance for the dissolution and leaching of carbonate minerals during increased rainy periods, and the increase of halite saturation during lesser rainfall period. AQUACHEM mixing studies suggested that geochemical signatures of 2006 and 2011 were preserved in samples of 2016 in different proportions. Considering the major factors, the main processes prevailing in the study area were inferred to be dissolution and leaching during 2006~2011 years and seawater intrusion along with ion exchange during 2011~2016 years. In all these periods of study, anthropogenic impact was also identified in the groundwater samples. Hence, this study revealed that the rainfall and water level gave a significant variation in the geochemical process of groundwater in the coastal aquifer system.
A novel technique was employed to optimize the CO2 sorption performance of spent shale at elevated pressure-temperature (PT) conditions. Four samples of spent shale prepared from the pyrolysis of oil shale under an anoxic condition were further modified with diethylenetriamine (DETA) and ethylenediamine (EDA) through the impregnation technique to investigate the variations in their physicochemical characteristics and sorption performance. The textural and structural properties of the DETA- and EDA- modified samples revealed a decrease in the surface area from tens of m2/g to a unit of m2/g due to the amine group dispersing into the available pores, but the pore sizes drastically increased to macropores and led to the creation of micropores. The N-H and C-N bonds of amine noticed on the modified samples exhibit remarkable affinity for CO2 sequestration and are confirmed to be thermally stable at higher temperatures by thermogravimetric (TG) analysis. Furthermore, the maximum sorption capacity of the spent shale increased by about 100% with the DETA modification, and the equilibrium isotherm analyses confirmed the sorption performance to support heterogenous sorption in conjunction with both monolayer and multilayer coverage since they agreed with the Sips, Toth, Langmuir, and Freundlich models. The sorption kinetics confirm that the sorption process is not limited to diffusion, and both physisorption and chemisorption have also occurred. Furthermore, the heat of enthalpy reveals an endothermic reaction observed between the CO2 and amine-modified samples as a result of the chemical bond, which will require more energy to break down. This investigation reveals that optimization of spent shale with amine functional groups can enhance its sorption behavior and the amine-modified spent shale can be a promising sorbent for CO2 sequestration from impure steams of the natural gas.