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.

Co-occurrence, possible origin, and health-risk assessment of arsenic and fluoride in drinking water sources in Mexico: Geographical data visualization.

Arsenic and fluoride in drinking water present a significant challenge to public health worldwide. In this study, we analyze the results of one of the largest surveys of drinking water quality in Mexico: 14,058 samples from 3951 sites, collected between January and December 2017. We use these data to identify the distribution and possible origin of arsenic and fluoride in drinking water throughout the country, and to estimate the associated health burden. The highest concentrations appear in alluvial aquifers in arid northern Mexico, where high-silica volcanic rock likely releases both arsenic and fluoride to the groundwater. We find fluoride contamination to be significantly correlated with aridity (Pearson correlation = -0.45, p = 0.0105), and also find a significant difference in fluoride concentrations between arid and humid states (Welch's t-test, p = 0.004). We estimate population exposure by assigning to each town in Mexico the average concentration of any sampling sites within 5 km. Our results show that 56% of the Mexican population lives within 5 km of a sampling site, 3.05 million people are exposed to fluoride above the reference dosage of 0.06 mg/(kg ∗ day), 8.81 million people are exposed to arsenic above the limit of 10 µg/L, and an additional 13,070 lifetime cases of cancer are expected from this arsenic exposure alone. This burden of disease is concentrated in the arid states of north-central Mexico.

An overview of nitrate sources and operating processes in arid and semiarid aquifer systems.

Nitrate concentration in most aquifers in arid and semi-arid areas has increased in the past several decades as a result of human activities. Under the predominantly oxic conditions of these aquifers, denitrification is inhibited, allowing nitrate, a soluble and stable form of nitrogen (N), to accumulate. Because of its close association with municipal and agricultural wastes, nitrate is commonly used as an indicator of anthropogenic contamination. Aquifers affected by agricultural waste may contain salts from irrigation returns and herbicides in addition to nitrates. Preventing leakage from soil to deeper parts of the aquifer is thus a priority in the sustainable management of aquifers in arid and semiarid areas. Studies report a wide range of nitrate concentrations distributed non-uniformly within the aquifer, with roughly 40% and 20% of sampled wells exceeding 50mg/L nitrate in shallow and deep parts of the aquifer respectively. In aquifers at risk of becoming contaminated, nitrate isotopes (δ15N, δ18O, Δ17O) can be used to identify the source of nitrogen as mineral or organic fertilizer, sewage, or atmospheric deposition. A variety of mathematical models (crop, hydrological, geochemical, or a combination of them) have been successful in identifying best practices that minimize N leakage without negatively affecting crop yield. In addition, field research in crop management, e.g., conservation agriculture, has yielded promising results in determining the adequate dosage and time of application of fertilizers to reduce N losses. Examples of key dryland aquifers impacted by nitrate are discussed, and some of the most pressing challenges to achieve sustainability are presented.

Abandoned PbZn mining wastes and their mobility as proxy to toxicity: A review.

Lead and zinc (PbZn) mines are a common occurrence worldwide; and while approximately 240 mines are active, the vast majority have been abandoned for decades. Abandoned mining wastes represent a serious environmental hazard, as Pb, Zn and associated metals are continuously released into the environment, threatening the health of humans and affecting ecosystems. Iron sulfide minerals, when present, can form acid mine drainage and increase the toxicity by mobilizing the metals into more bioavailable forms. Remediation of the metal waste is costly and, in the case of abandoned wastes, the responsible party(ies) for the cleanup can be difficult to determine, which makes remediation a complex and lengthy process. In this review, we provide a common ground from a wide variety of investigations about concentrations, chemical associations, and potential mobility of Pb, Zn and cadmium (Cd) near abandoned PbZn mines. Comparing mobility results is a challenging task, as instead of one standard methodology, there are 4-5 different methods reported. Results show that, as a general consensus, the metal content of soils and sediments vary roughly around 1000mg/kg for Zn, 100 for Pb and 10 for Cd, and mobilities of Cd>Zn>Pb. Also, mobility is a function of pH, particle size, and formation of secondary minerals. New and novel remediation techniques continue to be developed in laboratories but have seldom been applied to the field. Remediation at most of the sites has consisted of neutralization (e.g. lime,) for acid mine discharge, and leveling followed by phytostabilization. In the latter, amendments (e.g. biochar, fertilizers) are added to boost the efficiency of the treatment. Any remediation method has to be tested before being implemented as the best treatment is site-specific. Potential treatments are described and compared.

Assessing the State of Contamination in a Historic Mining Town Using Sediment Chemistry.

The United States town of Aurora, Missouri, USA, stockpiled lead (Pb) and zinc (Zn) mining wastes from the early to mid-1900s in the form of chat piles. Clean-up actions were undertaken at intervals in subsequent years including land leveling and removal of chat. This study assessed the current state of contamination by identifying areas where metals are present at toxic levels. For this purpose, stream sediment samples (N = 100) were collected over a 9 × 12 km area in and around Aurora. Their content of cadmium (Cd), Pb, and Zn were measured, and concentration maps were generated using ArcGIS to categorize affected areas. Metal concentrations varied over a wide range of values with the overall highest values observed in the north-northeast part of Aurora where abundant chat piles had been present. Comparison between observed concentrations and sediment-quality guidelines put the contaminated areas mentioned are above-toxic levels for Cd, Pb and Zn. In contrast, levels in rural areas and the southern part of Aurora were at background levels, thus posing no threat to aquatic habitats. The fact that contamination is constrained to a relatively small area can be advantageously used to implement further remediation and, by doing so, to help protect the underlying karst aquifer.

State of remediation and metal toxicity in the Tri-State Mining District, USA.

Mining operations in the Tri-State Mining District of Kansas, Missouri and Oklahoma (TSMD), once one of the major lead and zinc mining areas in the world, had completely ceased by 1970. As mining companies moved out, the land was left with underground tunnels and mine shafts and the surface with abandoned tailings piles, which progressively contaminated groundwater and soil. Despite remedial actions undertaken in the 1980's, areas within the TSMD still contain Cd, Pb, and Zn concentrations exceeding safe levels. Because of the large area and highly dispersed occurrence of wastes, environmental studies generally have been confined either to a stream basin or to a single state. Studies also have differed in their approach and analytical methodologies. An overview of the totality of the TSMD and its present state of contamination is presented here. Data show that metal content in sediments have the following common features: (1) a wide range of Pb and Zn concentrations, up to three orders of magnitude, (2) median values for Cd, Pb and Zn content in sediments and soils were similar among studies, (3) median values for most studies were at or above the guidelines recommended for aquatic habitats, and (4) highest content of Pb and Zn were closely associated with the geographical location of former mining and smelting centers. The above observations imply that mine wastes remain a problem and further remediation is needed. Cost-effective remedial alternatives for this area's geology, climate, and land use, are discussed.

Arsenic and fluoride variations in groundwater of an endorheic basin undergoing land-use changes.

The salt content of soil and water in endorheic basins within arid areas greatly restrict agricultural activities. Despite this limitation, these lands are increasingly used to accommodate new settlements and/or agricultural practices. This study focuses on the Laguna El Cuervo closed basin of northern Mexico and its underlying aquifer, which has been found to contain high concentrations of arsenic (As) and fluoride (F). The spatial distribution of As and F, their variations with time, and the impact of drought conditions and land-use changes were investigated using well data collected from a total of 27 wells in 2007, 2010, and 2011 (As data also collected in 2005). Four of these wells were used as monitoring wells. Data also included the As content of 140 surface sediments. Results showed that 54.5 % of the wells surpassed the As limit for drinking water of 0.025 mg L(-1) and that 89.0 % surpassed he F limit of 1.5 mg L(-1). Spatial analyses identified the areas in the center of the basin with the highest content of contaminants. Principal component and correlation analyses showed a co-occurrence of As and F with r = 0.55 for the 2011 data and 0.59 for the combined data. In contrast, the relationship of As and F concentrations to droughts and changes in land use were not as clearly shown, possibly because of the short time this area has been monitored. The high As and F concentrations in the groundwater may be limiting the availability of water within this basin, especially considering the greater groundwater demand foreseen for the future. Water-conservation practices, such as drip irrigation and artificial groundwater recharge, should be considered to maintain groundwater levels supportive of agricultural practices.

Co-occurrence of arsenic and fluoride in groundwater of semi-arid regions in Latin America: genesis, mobility and remediation.

Several million people around the world are currently exposed to excessive amounts of arsenic (As) and fluoride (F) in their drinking water. Although the individual toxic effects of As and F have been analyzed, there are few studies addressing their co-occurrences and water treatment options. Several studies conducted in arid and semi-arid regions of Latin America show that the co-occurrences of As and F in drinking water are linked to the volcaniclastic particles in the loess or alluvium, alkaline pH, and limited recharge. The As and F contamination results from water-rock interactions and may be accelerated by geothermal and mining activities, as well as by aquifer over-exploitation. These types of contamination are particularly pronounced in arid and semi-arid regions, where high As concentrations often show a direct relationship with high F concentrations. Enrichment of F is generally related to fluorite dissolution and it is also associated with high Cl, Br, and V concentrations. The methods of As and F removal, such as chemical precipitation followed by filtration and reverse osmosis, are currently being used at different scales and scenarios in Latin America. Although such technologies are available in Latin America, it is still urgent to develop technologies and methods capable of monitoring and removing both of these contaminants simultaneously from drinking water, with a particular focus towards small-scale rural operations.

Occurrence and treatment of arsenic in groundwater and soil in northern Mexico and southwestern USA.

This review focuses on the occurrence and treatment of arsenic (As) in the arid region of northern Mexico (states of Chihuahua and Coahuila) and bordering states of the southwestern US (New Mexico, Arizona, and Texas), an area known for having high As concentrations. Information assembled and assessed includes the content and probable source of As in water, soil, and sediments and treatment methods that have been applied in the area. High As concentrations were found mainly in groundwater, their source being mostly from natural origin related to volcanic processes with significant anthropogenic contributions near mining and smelting of ores containing arsenic. The affinity of As for solid phases in alkaline conditions common to arid areas precludes it from being present in surface waters, accumulating instead in sediments and shifting its threat to its potential remobilization in reservoir sediments and irrigation waterways. Factors such as oxidation and pH that affect the mobility of As in the subsurface environment are mentioned. Independent of socio-demographic variables, nutritional status, and levels of blood lead, cognitive development in children is being affected when exposed to As. Treatments known to effectively reduce As content to safe drinking water levels as well as those that are capable of reducing As content in soils are discussed. Besides conventional methods, emergent technologies, such as phytoremediation, offer a viable solution to As contamination in drinking water.

Contamination of the Conchos River in Mexico: does it pose a health risk to local residents?

Presently, water contamination issues are of great concern worldwide. Mexico has not escaped this environmental problem, which negatively affects aquifers, water bodies and biodiversity; but most of all, public health. The objective was to determine the level of water contamination in six tributaries of the Conchos River and to relate their levels to human health risks. Bimonthly samples were obtained from each location during 2005 and 2006. Physical-chemical variables (temperature, pH, electrical conductivity (EC), Total solids and total nitrogen) as well as heavy metals (As, Cr, Cu, Fe, Mn, Ni, V, Zn, and Li) were determined. The statistical analysis considered yearly, monthly, and location effects, and their interactions. Temperatures differed only as a function of the sampling month (P < 0.001) and the pH was different for years (P = 0.006), months (P < 0.001) and the interaction years x months (P = 0.018). The EC was different for each location (P < 0.001), total solids did not change and total nitrogen was different for years (P < 0.001), months (P < 0.001) and the interaction years x months (P < 0.001). The As concentration was different for months (P = 0.008) and the highest concentration was detected in February samples with 0.11 mg L(-1). The Cr was different for months (P < 0.001) and the interaction years x months (P < 0.001), noting the highest value of 0.25 mg L(-1). The Cu, Fe, Mn, Va and Zn were different for years, months, and their interaction. The highest value of Cu was 2.50 mg L(-1); for Fe, it was 16.36 mg L(-1); for Mn it was 1.66 mg L(-1); V was 0.55 mg L(-1); and Zn was 0.53 mg L(-1). For Ni, there were differences for years (P = 0.030), months (P < 0.001), and locations (P = 0.050), with the highest Ni value being 0.47 mg L(-1). The Li level was the same for sampling month (P < 0.001). This information can help prevent potential health risks in the communities established along the river watershed who use this natural resource for swimming and fishing. Some of the contaminant concentrations found varied from year to year, from month to month and from location to location which necessitated a continued monitoring process to determine under which conditions the concentrations of toxic elements surpass existing norms for natural waters.

Heavy metals in water of the San Pedro River in Chihuahua, Mexico and its potential health risk.

The objective of this study was to determine the seasonal and downstream water quality variations of the San Pedro River in Chihuahua, Mexico. Water samples were collected monthly from October 2005 to August 2006 in triplicate, totaling 165 water samples. The five sampling locations were: below the Francisco I. Madero dam (LP); between Rosales and Delicias (RD); Meoqui (M); El Torreon (ET), and Julimes (LJ). The levels of As, Be, Ca, Cd, Co, Cu, Cr, Fe, Li, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sr, Ti, Ta, V and Zn were measured using an Inductively Coupled Plasma- Optical Emission Spectrometry (ICP-OES) Perkin Elmer 2100. In addition, temperature, pH, electrical conductivity and total and fecal coliformes were determined. The statistical analysis considered a factorial treatment design; where factor A was the location point and factor B was sampling date. In addition, a multivariate technique looking for principal components was performed. The results indicated that some samples exceeded Mexican standards for As, Be, Ca, Cd, Co, Cr, Fe, Mn, Ni, Pb, Sb, Se, Sr and Zn. The As level must be considered for a red flag to the communities along the Rio San Pedro because both the monthly average level (0.10 mg L-1) and location (0.10 mg L-1) exceeded the Mexican and International norms. The multivariate analysis showed a predominant aggregation at the LP location, meaning that there was a predominance of As, Sr, Fe and Li. At the rest of the locations the elements did not present a tendency for aggregation. Statistics applied to sampling month showed that December, January, March and April were aggregated in a negative quadrant of component 1 indicating a predominance of V, Ni, Be, Fe and As. Overall, the results confirmed that this stretch of the San Pedro River is contaminated with heavy metals and other contaminants that might affect human health as well as the health of the ecosystem.