Nitrate sources and transformation processes in groundwater of a coastal area experiencing various environmental stressors.

In coastal salinized groundwater systems, contamination from various nitrate (NO3) inputs combined with complex hydrogeochemical processes make it difficult to distinguish NO3 sources and identify potential NO3 transformtation processes. Effective field-based NO3 studies in coastal areas are needed to improve the understanding of NO3 contamination dynamics in groundwater of such complex coastal systems. This study focuses on a typical Mediterranean coastal agricultural area, located in Tunisia, experiencing substantial NO3 contamination from multiple anthropogenic sources. Here, multiple isotopic tracers (δ18OH2O, δ2HH2O, δ15NNO3, δ18ONO3, and δ11B) combined with a Bayesian isotope MixSIAR model are used (i) to identify the major NO3 sources and their contributions, and (ii) to describe the potential NO3 transformation processes. The measured NO3 concentrations in groundwater are above the natural baseline threshold, suggesting anthropogenic influence. The measured isotopic composition of NO3 indicates that manure, soil organic matter, and sewage are the potential sources of NO3, while δ11B values constrain the NO3 contamination to manure; a finding that is supported by the results of MixSIAR model revealing that manure-derived NO3 dominates over other likely sources. Nitrate derived from manure in the study area is attributed to organic fertilizers used to promote crop growth, and livestock that deposit manure directly on the ground surface. Evidence for ongoing denitrification in groundwaters of the study area is supported by an enrichment in both 15N and 18O in the remaining NO3, although isotopic mass balances between the measured and the theoretical δ18ONO3 values also suggest the occurrence of nitrification. The simultaneous occurrence of these biogeochemical processes with heterogeneous distribution across the study area reflect the complexity of interactions within the investigated coastal aquifer. The multiple isotopic tracer approach used here can identify the effect of multiple NO3 anthropogenic activities in coastal environments, which is fundamental for sustainable groundwater resources management.

Predicting geogenic arsenic contamination in shallow groundwater of south Louisiana, United States.

Groundwater contaminated with arsenic (As) threatens the health of more than 140 million people worldwide. Previous studies indicate that geology and sedimentary depositional environments are important factors controlling groundwater As contamination. The Mississippi River delta has broadly similar geology and sedimentary depositional environments to the large deltas in South and Southeast Asia, which are severely affected by geogenic As contamination and therefore may also be vulnerable to groundwater As contamination. In this study, logistic regression is used to develop a probability model based on surface hydrology, soil properties, geology, and sedimentary depositional environments. The model is calibrated using 3286 aggregated and binary-coded groundwater As concentration measurements from Bangladesh and verified using 78 As measurements from south Louisiana. The model's predictions are in good agreement with the known spatial distribution of groundwater As contamination of Bangladesh, and the predictions also indicate high risk of As contamination in shallow groundwater from Holocene sediments of south Louisiana. Furthermore, the model correctly predicted 79% of the existing shallow groundwater As measurements in the study region, indicating good performance of the model in predicting groundwater As contamination in shallow aquifers of south Louisiana.

Human-induced pollution and toxicity of river sediment by potentially toxic elements (PTEs) and accumulation in a paddy soil-rice system: A comprehensive watershed-scale assessment.

This study aimed to assess pollution by potentially toxic elements (PTEs) in the Zarjoub and Goharroud river basins in northern Iran. Due to exposure to various types of pollution sources, these rivers are two of the most polluted rivers in Iran. They also play an important role in irrigation of paddy fields in the study area, increasing concerns about the contamination of rice grains by PTEs. Hence, we analyzed the concentrations of eight PTEs (i.e., As, Co, Cr, Cu, Mn, Ni, Pb, and Zn) at ten channel bed sediment sampling sites in each river, fifteen samples of paddy soils and fifteen co-located rice samples in the relevant watersheds. Results of the index-based assessment indicate moderate to heavy pollution and moderate toxicity for sediments in the Goharroud River, while both pollution and toxicity of the Zarjoub River sediment were characterized as moderate. Paddy soils in the watersheds were found to be moderate to heavily polluted by PTEs, but the values of the rice bioconcentration factor (RBCF) indicated intermediate absorption for Cu, Zn, and Mn, and weak and very weak absorption for Pb/Ni and As/Co/Cr, respectively. The concentration of Zn, Cu, Pb, and Cr was negatively correlated to the corresponding values of RBCF, highlighting the ability of rice grains to control bioaccumulation and regulate concentrations. Industrial/agricultural effluents, municipal wastewater, leachate of solid waste, traffic-related pollution, and weathering of parent materials were found to be responsible for pollution of the Zarjoub and Goharroud watersheds by PTEs. Mn, Cu, and Pb in rice grains might be responsible for non-carcinogenic diseases. Although weak absorption was observed for As and Cr in rice grains, the concentrations of these elements in rice grains indicate a high level of cancer risk if ingested. This study provides insights to control the pollution of sediment, paddy soils, and rice.

Phytoremediation capability of Typha latifolia L. to uptake sediment toxic elements in the largest coastal wetland of the Persian Gulf.

The present study evaluated the status of sediment toxicity and pollution, and the phytoremediation capability of Typha latifolia L. (TlL) within the largest coastal wetland in the southwest of Iran, the Shadegan International Wetland. In eight sampling sites, covering the entire wetland, the concentration of six toxic elements (As, Cr, Cu, Ni, Pb, and Zn) in the surface sediment, root, and stem of TlL were measured. The results indicated that mean concentrations of Cr, Cu, Pb, and Zn were found to be higher than those in the local background, which likely indicates anthropogenic sources of these elements. Due to the presence of a nearby landfill, the results of modified pollution index (MPI) and aggregate toxicity index (ATI) indicated a moderately-heavily polluted level and moderate to high toxic degree, respectively. However, the medium-low level of toxicity toward living of organisms (21 % probability) was detected based on the assessment of the Sediment Quality Guidelines (SGQ). The results of our study indicate that the root and stem tissues of TlL are capable of acting as an indicator of Cu/Pb/Zn and Zn pollution in sediment, respectively. Considering the potential of phytoremediation, TlL represented both phytostabilization and phytoextraction capabilities for Pb and Zn and a significant increase was observed in the phytoremediation capability by increasing the distance from the landfill area. According to the results of the metal accumulation index (MAI) and comprehensive bioconcentration index (CBCI), TlL grown in the study area showed an acceptable performance in the accumulation of multiple toxic elements compared to that in Turkey, India, and Poland. Overall, TlL is a good candidate for the phytoremediation of sediments contaminated by Pb and Zn.

Potential impacts of titanium dioxide nanoparticles on trace metal speciation in estuarine sediments.

Engineered titanium dioxide (TiO2) nanoparticles (NPs) are widely used and consequently released into the environment. The subsequent accumulation of TiO2 NPs in depositional environments may affect the geochemical behavior of trace metals, which needs to be assessed. Here, we performed experiments to investigate the speciation change for molybdenum and tungsten in the presence of TiO2 NPs. Laboratory results show that the rate constant for MoS42- hydrolysis associated with TiO2 NPs is ~1.75 × 10-9 L m-2 s-1, whereas it is 5.95 × 10-10 L m-2 s-1 for WS42- hydrolysis. In addition, we estimated the maximum rate for MoS42- hydrolysis to be ~1.24 × 10-1 µM hr-1, whereas the maximum rate for WS42- hydrolysis is ~4.91 × 10-2 µM hr-1. However, the modeling results suggest that the TiO2 NPs accumulated in estuarine sediments might play a relatively minor role in affecting the speciation of trace metals prior to the current time. This is because the relatively low accumulation (i.e., < 8 × 10-3 mol kg-1) of TiO2 NPs before 2021 results in the lower rate (>100 times) for speciation changes of both molybdenum and tungsten compared to the rate for natural geochemical processes. On the other hand, our results suggest that TiO2 NPs will likely impact the oxyanion cycling in the near future owing to the increasing accumulations of TiO2 NPs in estuarine sediments.

Chloride-salinity as indicator of the chemical composition of groundwater: empirical predictive model based on aquifers in Southern Quebec, Canada.

The present study first describes the variations in concentrations of 12 chemical elements in groundwater relative to salinity levels in Southern Quebec (Canada) groundwater systems, and then uses this data to develop an empirical predictive model for evaluating groundwater chemical composition relative to salinity levels. Data is drawn from a large groundwater chemistry database containing 2608 samples. Eight salinity classes were established from lowest to highest chloride (Cl) concentrations. Graphical analyses were applied to describe variations in major, minor, and trace element concentrations relative to salinity levels. Results show that the major elements were found to be dominant in the lower salinity classes, whereas Cl becomes dominant at the highest salinity classes. For each of the major elements, a transitional state was identified between domination of the major elements and domination of Cl. This transition occurred at a different level of salinity for each of the major elements. Except for Si, the minor elements Ba, B, and Sr generally increase relative to the increase of Cl. The highest Mn concentrations were found to be associated with only the highest levels of Cl, whereas F was observed to be more abundant than Mn. Based on this analysis of the data, a correlation table was established between salinity level and concentrations of the chemical constituents. We thus propose a predictive empirical model, identifying a profile of the chemical composition of groundwater relative to salinity levels, to help homeowners and groundwater managers evaluate groundwater quality before resorting to laborious and costly laboratory analyses.

Groundwater geochemistry, quality, and pollution of the largest lake basin in the Middle East: Comparison of PMF and PCA-MLR receptor models and application of the source-oriented HHRA approach.

We evaluated groundwater quality, pollution, and its effects on human health in the eastern part of the Lake Urmia basin, the largest lake in the Middle East. Although groundwater quality is suitable for drinking and irrigation purposes, an index-based approach quantifying heavy metal pollution revealed that most sampling sites exhibited moderate to high pollution levels in the northern and southern regions. The positive matrix factorization (PMF) and principal component analysis-multi linear regression (PCA-MLR) receptor models suggest that the main contributors to the observed groundwater pollution, expressed as percentages by model, were: lake water infiltration and dissolution of minerals and fertilizers (46% and 63%), infiltration of leachates from solid wastes (29% and 15%), mixing with industrial-municipal wastewaters (18% and 13%), and vehicular emissions (7% and 9%). The PMF model indicated better correlations between observed and predicted concentrations (R2 = 0.96) than the PCA-MLR (R2 = 0.89). Our results from the human health risk assessments (HHRA) highlight non-carcinogenic and carcinogenic risks for Pb and Cr, respectively. Also, the PMF-based assessment of human health risk indicated that wastewaters and solid waste leachates are responsible for the cancer risk from Cr for children.

Combined effects of seawater intrusion and nitrate contamination on groundwater in coastal agricultural areas: A case from the Plain of the El-Nil River (North-Eastern Algeria).

This study focuses on coastal aquifers subject to uncontrolled land use development by investigating the combined effects of seawater intrusion and nitrate contamination. The research is undertaken in a Mediterranean coastal agricultural area (Plain of the El-Nil River, Algeria), where water resources are heavily impacted by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ2HH2O, δ18OH2O, δ15NNO3 and δ18ONO3), is combined with a hydrochemical facies evolution diagram, and a Bayesian isotope mixing model (MixSIAR) to assess seawater contamination with its inland intrusion, and distinguish the nitrate sources and their apportionment. Results show that seawater intrusion is circumscribed to the sector neighboring the Mediterranean Sea, with two influencing functions including classic inland intrusion through the aquifer, and upstream seawater impact through the river mouth connected to the Mediterranean Sea. Groundwater and surface water samples reveal nitrate concentrations above the natural baseline threshold, suggesting anthropogenic influence. Results from nitrate isotopic composition, NO3 and Cl concentrations, and the MixSIAR model show that nitrate concentrations chiefly originate from sewage and manure sources. Nitrate derived from the sewage is related to wastewater discharge, whereas nitrate derived from the manure is attributed to an excessive use of animal manure to fertilise agricultural areas. The dual negative impact of seawater intrusion and nitrate contamination degrades water quality over a large proportion of the study area. The outcomes of this study are expected to contribute to effective and sustainable water resources management in the Mediterranean coastal area. Furthermore, this study may improve scientists' ability to predict the combined effect of various anthropogenic stressors on coastal environments and help decision-makers elsewhere to prepare suitable environmental strategies for other regions currently undergoing an early stage of water resources deterioration.

Multi-tracer approach to understand nitrate contamination and groundwater-surface water interactions in the Mediterranean coastal area of Guerbes-Senhadja, Algeria.

Implementing sustainable groundwater resources management in coastal areas is challenging due to the negative impacts of anthropogenic stressors and various interactions between groundwater and surface water. This study focuses on nitrate contamination and transport via groundwater-surface water exchange in a Mediterranean coastal area (Guerbes-Senhadja region, Algeria) that is heavily affected by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ2HH2O, δ18OH2O, 3H, δ15NNO3 and δ18ONO3), is combined with a Bayesian isotope mixing model (MixSIAR) to (i) elucidate the nitrate sources and their apportionments in water systems, and (ii) describe potential interactions between groundwater and surface water. Results from nitrate isotopic composition and the MixSIAR model show that nitrate concentrations mainly originate from sewage and manure sources. Nitrate derived from the sewage is attributed to urban and rural wastewater discharge, whereas nitrate derived from the manure is related to animal manure used to fertilise agricultural areas. High apportionments of nitrate-based atmospheric precipitation are identified in groundwater and surface water; a finding that is specific to this study. The multi-origin stresses combined with evidence of interactions between surface water and groundwater contribute to negatively impacting large parts of the study coastal area. The outcomes of this study are expected to contribute to sustainable management of coastal ecosystems by drawing more attention towards groundwater use and protection. Furthermore, this study may improve scientists' ability to predict the behavior of anthropogenically impacted coastal ecosystems and help decision-makers elsewhere to prepare suitable environmental strategies for other coastal ecosystems currently undergoing an early stage of groundwater resources deterioration.

Lanthanide rarity in natural waters: implications for microbial C1 metabolism.

Research in the last decade has illuminated the important role that lanthanides play in microbial carbon metabolism, particularly methylotrophy. Environmental omics studies have revealed that lanthoenzymes are dominant in some environments, and laboratory studies have shown that lanthoenzymes are favored over their calcium-containing counterparts even when calcium is far more abundant. Lanthanide elements are common in rocks but occur at exceedingly low levels in most natural waters (picomolar to nanomolar range) with the exception of volcanic hot springs, which can reach micromolar concentrations. Calcium is orders of magnitude higher in abundance than lanthanide elements across natural settings. Bacteria that use lanthanides for growth on simple carbon compounds (e.g. methanol and ethanol) grow optimally at micromolar concentrations. It is highly likely that bacteria in the environment have evolved specialized lanthanide sequestration and high-affinity uptake systems to overcome lanthanide deprivation. Indeed, we identified genes in soil metagenomes encoding the lanthanide-binding protein lanmodulin, which may be important for cellular differentiation between calcium and lanthanides. More research is needed on microbial adaptations to lanthanide scarcity.

Origin of tungsten and geochemical controls on its occurrence and mobilization in shallow sediments from Fallon, Nevada, USA.

Tungsten (W) occurrence and speciation was investigated in sediments collected from Fallon, Nevada where previous studies have linked elevated W levels in human body fluids to an unusual cluster of childhood leukemia cases. The speciation of sedimentary W was determined by µ-XRF mapping and µ-XANES. The W content of the analyzed surface sediments ranged between 81 and 25,908 mg/kg, which is significantly higher than the W content in deeper sediments which ranged from 37 to 373 mg/kg at 30 cm depth. The µ-XANES findings reveal that approximately 20-50% of the total W in the shallow sediment occurs in the metallic form (W0); the rest occurs in the oxide form (WVIO3). Because W0 does not occur naturally, its elevated concentrations in surface sediments point toward a possible local anthropogenic origin. The oxidation of metallic W0 with meteoric waters likely leads to the formation of WVIO3. The chief water-soluble W species was identified as WO42- by chromatographic separation and speciation modeling. These results led us to postulate that W0 particles from a currently unknown but local source(s) is (are) deposited onto the soils and/or surface sediments. The W0 in interaction with meteoric water is oxidized to WVIO3, and as these sediment-water interactions progress, WO42- is formed in the water at pH ∼7. Under pH < 7, and sufficient W concentrations, tungstate tends to polymerize, and polymerized species are less likely to adsorb onto sediments. Polymerized species have lower affinity than monomers, which leads to enhanced mobility of W.

Evaluating mobilization and transport of arsenic in sediments and groundwaters of Aquia aquifer, Maryland, USA.

Groundwater and sediment samples were collected along a flow path in the Aquia aquifer (Paleocene), Maryland in order to examine and study the factors influencing "evolution" of arsenic (As) in these groundwaters. The Aquia crops out near Washington, DC, where it is unconfined, and extends approximately 90 km down dip to the south and east towards and beneath the Chesapeake Bay. The studied flow path was chosen owing to (i) the number of accessible wells, (ii) differences in total dissolved As concentrations in groundwaters from some of the sampled wells, which reach values > or =667 nmol kg(-1) or > or =50 ppb, and (iii) the distinct difference in total dissolved As concentrations in Aquia groundwaters between the northern and southern portions of the study area. In groundwater samples, in situ separation of inorganic As species [As(III) and As(V)] were performed by using anion exchange chromatography. Subsequently, As concentrations were determined by inductively coupled plasma mass spectrometry. In situ measurements of Fe concentrations and speciation, dissolved S(-II) concentrations, pH, alkalinity, and oxidation-reduction potential (Eh) were determined to establish the oxidation-reduction conditions and solution chemistry along the flow path. Concentrations of As in 12 analyzed groundwater samples range from approximately 0.75 to 1 072 nmol kg(-1), and As(III) concentrations ranging from 0.24 to 980 nmol kg(-1) appears to be the dominant form of As in solution. 50% of the studied wells yielded groundwaters with concentrations that exceed the US EPA's Maximum Contaminant Level for As in drinking water of 133 nmol kg(-1) or 10 ppb. In order to examine the solid phase speciation of As within the aquifer sediments, we collected a number of Aquia sediment samples from a drill core that was archived at the Maryland Geological Survey. These sediment samples were evaluated using a previously established sequential extractions procedure. Solid phase As concentrations range between 973 and 2,012 nmol kg(-1). Additionally, petrographic, X-Ray diffraction and diffuse reflectance spectroscopy analyses of the Aquia sediments reveal presence of glauconite, and smectite along with goethite and hematite within the samples. Here, we present the possible mechanisms responsible for the elevated As concentrations in the studied groundwaters of the Aquia aquifer.

Potential contaminants at a dredged spoil placement site, Charles City County, Virginia, as revealed by sequential extraction.

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.

Chemical and colloidal analyses of natural seep water collected from the exploratory studies facility inside Yucca Mountain, Nevada, USA.

Yucca Mountain is being considered as a geological repository for the USA's spent nuclear fuel and high-level nuclear waste. Numerous groundwater seeps appeared during March 2005 within the exploratory studies facility (ESF), a tunnel excavated in the mountain. Because of the relevance to radionuclide transport and unsaturated zone-modeling studies, we analyzed the seep samples for major anions and cations, rare earth elements, and colloids. Major ion species and elemental concentrations in seep samples reflect interaction of the water with the volcanic rock and secondary calcites. Elemental fractograms from flow-injection field-flow fractionation ICP-MS scans detected Br, Ca, Cl, Cu, Fe, I, Mg, Si, Sr, W, and U at void fractions, suggesting they may be present in the form of dissolved anions. Colloids approximately 10 nm in hydrodynamic diameter, possibly calcite, were also present in the seepage samples. Geochemical calculations indicate, however, these may be an artifact (not present in the groundwater) which arose because of loss of CO2 during sample collection and storage.