In groundwater vulnerability assessment, spatial interpolation uses information on sample location points to predict and map the unsampled locations. Depending on their probabilistic nature, spatial interpolation techniques can be divided into deterministic (e.g., IDW) and geostatistical (e.g., Kriging) approaches. Ref.
employed disjunctive kriging (DK), along with ordinary kriging and cokriging, to assess the probability of non-point source groundwater contamination under the influence of agricultural land use. They collected groundwater samples according to the summer crop cycle from 2004 to 2006. The results indicate that interannual climate variation and fertilization control nitrate contamination. Therefore, from an agri-environmental perspective, this method can achieve a reliable outcome for the decision-makers. Ref.
employed ordinary point kriging to assess the spatiotemporal groundwater contamination in the Mediterranean region. They monitored the groundwater table depth and contours, pH, EC, and NO
during the pre-monsoon (June) and post-monsoon (October) seasons in 2009 and 2010 from 220 monitoring wells. The outcome reported how rainfall patterns can change the evapotranspiration pattern, which controls the amount of NO
leaching (higher temperature and lower relative humidity can increase evapotranspiration and minimize the risk of NO
leaching).
In the past decade, many multivariate analyses were conducted to analyze the spatiotemporal distribution of contaminants in the groundwater. Principal component analysis (PCA) is one of the most significant and widely used parameter-identifying tools and data reduction techniques for almost all environmental studies. It found that in the recent past, PCA integrated with factor analysis (FA), hierarchical cluster analysis (HCA), regressions, or spatial interpolation methods was intensively used in the vulnerability assessment of groundwater contamination. Ref.
[29] presented a GIS-based study by combining PCA and IDW to investigate the nitrogen sources in groundwater under various land use scenarios. Ref.
[30] combined PCA and FA to track the urban pollution source and the concentration level. FA was employed to reduce the involvement of less significant parameters within each component. This reduction procedure involved extracting a different set of varifactors by rotating the axes defined by the PCA extraction. A K-means-based cluster analysis (CA) was employed on the FA-extracted varifactors to analyze the similarities in the water quality. Ref.
[31] employed PCA to track the source and transport of chlorate in the groundwater under agricultural land use. Ref.
[32] investigated the spatiotemporal vulnerability of GW quality using a robust PCA (ROBPCA) method. To avoid the drawbacks of classical PCA (such as anomalous observations, overestimating the variance, etc.), they compared and proposed ROBPCA for the measurement of the seasonal and hydro-chemical characteristics of the aquifer. ROBPCA is a useful method for identifying spatiotemporal variations in GW quality when hydro-chemical processes are diverse and anomalous samples are available.
Regression Models
Ref.
[33] investigated nitrate contamination using the generalized additive mixed models (GAMMs) suggested by
[34]. These regression models are used primarily for spatiotemporal trend identification in complex monitoring data. Ref.
[35] employed a combined multiple regression and multi-tracer method to predict the spatiotemporal distribution of nitrate in the groundwater and the factors contributing to its sources. Time series (1980, 1995, and 2000) land use maps were used to estimate the land use pattern at the time of recharge of “young water”. This temporal analysis was conducted using the linear interpolation method
[36]. A simple material balance model
[37] was fitted to estimate the nitrate concentration mixed by different recharge sources given the known amount of water recharged into shallow aquifers.
Artificial Intelligence
Ref.
[38] proposed a feed-forward multilayer artificial neural network (ANN) to investigate the pollution sources in terms of duration of activity, magnitude, and location. A back propagation neural network (BPNN) was employed to identify the source characteristics. The Latin hypercube sampling (LHS) approach generated temporal varying source fluxes. These outputs were used in groundwater flow and the transport simulation model. The information generated through this process was used in the ANN model-building processes. Breakthrough curves (BTC) were also obtained for the specific contamination scenarios. The parameters of the BTC were used as inputs for the ANN model.
Spatial Autocorrelation
Ref.
[39] evaluated the spatiotemporal trend of fluoride concentration by combining two different statistical methods: Moran’s I
[40] and Local Indicators of Spatial Association (LISA)
[41]. LISA is a distance-based method that quantifies the extent of clustering of the high or low values of the parameter of interest and how the values in the neighboring locations vary within a specified bandwidth (distance). LISA provides a better indication of the clustering of the spatial units by calculating local Moran’s I for each unit.
Bayesian Networks
Ref.
[42] introduced an integrated approach to assess the time-dependent vulnerability of groundwater to non-point source contamination. A data-driven Bayesian method (weights of evidence (WofE)) was employed to determine the relationship between temporal changes in land use and GW pollution and to forecast future trends. Ref.
[43] introduced a new regret-based optimization model to identify the pollution source in the GW system. Groundwater flow and contaminant transport were calculated using MODFLOW and MT3D. A Monte Carlo analysis was employed to measure the impacts of risk and uncertainty in the model parameters and inputs. A Bayesian network model was trained and validated based on the outputs of the Monte Carlo analysis.
Other Statistical Methods
Ref.
[44] proposed a detailed decision tree with which to measure the lag time and transport of contaminants in the groundwater. This approach can map the GW vulnerability and comply with the management strategies suggested by the WFD and GWD. Ref.
[45] employed the PRACTICAL simulation model
[46] to investigate the relationship between nitrate occurrence and contextual variables, i.e., rainfall and recharge. PRACTICAL quantifies the monthly recharge amount by considering a set of contextual parameters in the calculations. Sequential Gaussian simulation was employed to generate simulated scenarios regarding nitrate concentration for each hydrological year to evaluate the values above and below the threshold of 50 mg-NO
3/1, and to determine the average of the simulated nitrate concentrations.
Physical/Process-Based Methods
The dynamic concept of GW vulnerability is mainly controlled by various surface and subsurface processes, such as spatial and temporal variation of GW recharge and its storage across multiple flow systems with different residence times. Therefore, these processes should be considered in a GW vulnerability assessment in order to better manage GW resources. Furthermore, processes-based methods can deal with the contaminant’s fate and transport, making them suitable for understanding how anthropogenic activities and climate change may affect this vital source
[13].
2.2. Karst Aquifer Vulnerability Assessment
Karst aquifers are one of the most important sources of fresh water, supplying water to fulfil the demand of 25% of the global population
[47]. These aquifers provide a significant amount of drinking water in Europe; for some regions, they are the only source of fresh water. The contamination vulnerability of these vital freshwater sources significantly threatens the vast population fulfilling their demand for drinking water. Karst aquifers are susceptible to hydrological changes in the recharge regions. Karst aquifers represent a unique hydrogeological process through the conduit (pipe-like flow system) and diffuse (through fractures and pores) flow systems
[13]. Due to these dual characteristics of karst systems, they present more pronounced surface and subsurface interrelationships, making them vulnerable to contaminants in two different ways. Fast travel time and low storage capacity in conduit flow make karsts sensitive to “short-lived” pollutants. On the other hand, in diffuse systems, “persistent” contaminants can be stored and released over a long period of time
[13]. Because of these unique vulnerability scenarios, karst aquifers need special attention regarding groundwater vulnerability assessment.
2.2.1. Overlay and Index-Based Method
Ref.
[48] evaluated intrinsic and specific vulnerability using the DRASTIC and DRASTIC Pesticide methods. A susceptibility index (SI) was also employed to visualize the temporal changes in specific vulnerability. Due to the typical sub-surface flow system in the karst aquifers, vertical seepage and lateral flow should be considered in order to map the karst groundwater vulnerability in terms of source and resource protection. Ref.
[49] measured the spatiotemporal groundwater contamination using the COP method. They integrated the geographically weighted regression (GWR) and used elevation, land-use, geology, and normalized differentiate vegetative index (NDVI) parameters to describe the spatial dynamics of relationships among the variables.
2.2.2. Statistical Method
Ref.
[50] developed a GIS tool integrated with the residence time distribution (RTD) model to measure the lumped parameters based on vulnerability mapping parameters. This method links the temporal groundwater quality with the vulnerability concept based on equivalent lumped parameters. This semi-objective method is based on the probability distribution of residence times and can represent a better groundwater vulnerability assessment for decision making.
2.2.3. Process-Based Method
Ref.
[13] drew the attention of the hydrogeologist to the variation in spatiotemporal groundwater recharge. They suggested that the consideration of movement tracking of groundwater flow and its discharge at various springs should become essential. It is, therefore, crucial to understand these processes in order to track the water storage and residence time in multiple systems. They suggested a numerical modeling technique for the broader understanding of dynamic karst aquifer vulnerability and its relationship with climate change to achieve better quantification. They employed the recharge, conduit flow, and diffuse flow (RCD) rainfall-discharge model, “RCD-seasonal”
[51], to simulate the discharge and substance concentration of the investigated spring. This is a lumped parameter model based on a conceptual model of the karst aquifer system where water flows through three main compartments: the recharge (soil and epikarst system), conduit/fast flow, and diffuse/slow flow systems.