Fluorescent Dissolved Organic Matter Components as Surrogates for Disinfection Byproduct Formation in Drinking Water: A Critical Review.

Disinfection byproduct (DBP) formation, prediction, and minimization are critical challenges facing the drinking water treatment industry worldwide where chemical disinfection is required to inactivate pathogenic microorganisms. Fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC) is used to characterize and quantify fluorescent dissolved organic matter (FDOM) components in aquatic systems and may offer considerable promise as a low-cost optical surrogate for DBP formation in treated drinking waters. However, the global utility of this approach for quantification and prediction of specific DBP classes or species has not been widely explored to date. Hence, this critical review aims to elucidate recurring empirical relationships between common environmental fluorophores (identified by PARAFAC) and DBP concentrations produced during water disinfection. From 45 selected peer-reviewed articles, 218 statistically significant linear relationships (R2 ≥ 0.5) with one or more DBP classes or species were established. Trihalomethanes (THMs) and haloacetic acids (HAAs), as key regulated classes, were extensively investigated and exhibited strong, recurrent relationships with ubiquitous humic/fulvic-like FDOM components, highlighting their potential as surrogates for carbonaceous DBP formation. Conversely, observed relationships between nitrogenous DBP classes, such as haloacetonitriles (HANs), halonitromethanes (HNMs), and N-nitrosamines (NAs), and PARAFAC fluorophores were more ambiguous, but preferential relationships with protein-like components in the case of algal/microbial FDOM sources were noted. This review highlights the challenges of transposing site-specific or FDOM source-specific empirical relationships between PARAFAC component and DBP formation potential to a global model.

Assessing antimicrobial and metal resistance genes in Escherichia coli from domestic groundwater supplies in rural Ireland.

Natural ecosystems can become significant reservoirs and/or pathways for antimicrobial resistance (AMR) dissemination, with the potential to affect nearby microbiological, animal, and ultimately human communities. This is further accentuated in environments that provide direct human exposure, such as drinking water. To date, however, few studies have investigated AMR dissemination potential and the presence of co-selective stressors (e.g., metals/metalloids) in groundwater environments of human health significance. Accordingly, the present study analysed samples from rural (drinking) groundwater supplies (i.e., private wells) in the Republic of Ireland, where land use is dominated by livestock grazing activities. In total, 48 Escherichia coli isolates tested phenotypically for antimicrobial susceptibility in an earlier study were further subject to whole genome sequencing (WGS) and corresponding water samples were further analysed for trace metal/metalloid concentrations. Eight isolates (i.e., 16.7%) were genotypically resistant to antimicrobials, confirming prior phenotypic results through the identification of ten antimicrobial resistance genes (ARGs); namely: aph(3″)-lb (strA; n=7), aph(6)-Id (strA; n = 6), blaTEM (n = 6), sul2 (n = 6), tetA (n = 4), floR (n = 2), dfrA5 (n = 1), tetB (n = 1), and tetY (n = 1). Additional bioinformatic analysis revealed that all ARGs were plasmid-borne, except for two of the six sul2 genes, and that 31.2% of all tested isolates (n = 15) and 37.5% of resistant ones (n = 3) carried virulence genes. Study results also found no significant relationships between metal concentrations and ARG abundance. Additionally, just one genetic linkage was identified between ARGs and a metal resistance gene (MRG), namely merA, a mercury-resistant gene found on the same plasmid as blaTEM, dfrA5, strA, strB, and sul2 in the only isolate of inferred porcine (as opposed to bovine) origin. Overall, findings suggest that ARG (and MRG) acquisition may be occurring prior to groundwater ingress, and are likely a legacy issue arising from agricultural practices.

The antimicrobial resistance profiles of Escherichia coli and Pseudomonas aeruginosa isolated from private groundwater wells in the Republic of Ireland.

The role of the natural environment in the dissemination of antimicrobial resistant bacteria has been increasingly recognised in the literature. However, knowledge surrounding the critical factors and mechanisms mediating their occurrence is still limited, particularly in relatively 'pristine' groundwater environments. In the Republic of Ireland (RoI), a country characterised by high groundwater reliance, household-based (unregulated) wells provide drinking water to 11% of the population. These private wells are generally located in rural areas, where the risk of microbiological contamination is high due to intensive agricultural practices and high reliance on domestic wastewater treatment systems; both of which are also potential sources of antimicrobials and antimicrobial resistant bacteria. Accordingly, the current research sought to elucidate current rates of antimicrobial resistant bacteria and the principal factors associated with their presence in private wells in the RoI. A total of 250 samples (from 132 wells nationwide) were assessed for the presence of faecal (Escherichia coli) and environmental (Pseudomonas aeruginosa) bacteria, with single isolates from each contaminated sample tested phenotypically against 18 and 9 antimicrobials, respectively. Findings show that while 16.7% of E. coli (n = 8/48) were categorically resistant to ≥1 antimicrobial, with a further 79.2% classified as intermediately resistant, no categorical resistance was found among P. aeruginosa isolates (n = 0/6), with just one intermediately resistant isolate detected. Multivariate regression modelling indicates significantly higher odds of resistant E. coli detection in concurrence with elevated cattle density (OR = 1.028, p = 0.032), aligning with findings of highest resistance rates to veterinary antimicrobials (e.g., streptomycin = 14.6%, tetracycline = 12.5%, and ampicillin = 12.5%). Multivariate model results also suggest overland flow culminating in direct wellhead ingress as a primary ingress mechanism for resistant E. coli. Study findings may inform groundwater source protection initiatives and antimicrobial resistance surveillance moving forward.

Spatiotemporal dynamics of Escherichia coli presence and magnitude across a national groundwater monitoring network, Republic of Ireland, 2011-2020.

Groundwater is a vital drinking water resource and its protection from microbiological contamination is paramount to safeguard public health. The Republic of Ireland (RoI) is characterised by the highest incidence of verocytotoxigenic Escherichia coli (VTEC) enteritis in the European Union (EU), linked to high reliance on unregulated groundwater sources (~16% of the population). Yet, the spatio-temporal factors influencing the frequency and magnitude of microbial contamination remain largely unknown, with past studies typically constrained to spatio-temporally 'limited' sampling campaigns. Accordingly, the current investigation sought to analyse an extensive spatially distributed time-series (2011-2020) of groundwater monitoring data in the RoI. The dataset, compiled by the Environmental Protection Agency (EPA), showed 'high' contamination rates, with 66.7% (88/132) of supplies testing positive for E. coli, and 29.5% (39/132) exceeding concentrations of 10MPN/100 ml (i.e. gross contamination) at least once during the 10-year monitoring period. Seasonal decomposition analyses indicate that E. coli detection rates peak during late autumn/early winter, coinciding with increases in annual rainfall, while gross contamination peaks in spring (May) and late-summer (August), likely reflecting seasonal shifts in agricultural practices. Mixed effects logistic regression modelling indicates that monitoring sources located in karst limestone are statistically associated with E. coli presence (OR = 2.76, p = 0.03) and gross contamination (OR = 2.54, p = 0.037) when compared to poorly productive aquifers (i.e., transmissivity below 10m2/d). Moreover, 5-day and 30-day antecedent rainfall increased the likelihood of E. coli contamination (OR = 1.027, p < 0.001 and OR = 1.005, p = 0.016, respectively), with the former also being associated with gross contamination (OR = 1.042, p < 0.001). As such, it is inferred that preferential flow and direct ingress of surface runoff are the most likely ingress mechanisms associated with E. coli groundwater supply contamination. The results presented are expected to inform policy change around groundwater source protection and provide insight for the development of groundwater monitoring programmes in geologically heterogeneous regions.

Groundwater resources as a global reservoir for antimicrobial-resistant bacteria.

Antimicrobial resistance represents one of our most significant global health threats, with increasing incidences noted in both clinical and environmental settings. As such, identifying and understanding the sources and pathways for antimicrobial-resistant bacteria (ARB) is critical. The current study presents the first systematic review and pooled analysis of ARB occurrence in global groundwater supplies, which are used as primary drinking water sources by 2.2 billion people worldwide and are recurrently linked to significant outbreaks of infection. Seventy peer-reviewed studies were identified and included; findings reveal that 80.2% ± 29.0 and 57.2% ± 36.8 of aggregated groundwater isolates were resistant to ≥1 and ≥3 antimicrobials, respectively. Where bacteria were present, ARB were identified in 76.9% ± 33.7 of individual wells and springs. Our results leave little doubt that groundwater represents a major global reservoir for ARB, however significant research is required to establish environmental determinants and mechanisms mediating their occurrence.

Revealing chlorinated ethene transformation hotspots in a nitrate-impacted hyporheic zone.

Hyporheic zones are increasingly thought of as natural bioreactors, capable of transforming and attenuating groundwater pollutants present in diffuse baseflow. An underappreciated scenario in the understanding of contaminant fate in hyporheic zones is the interaction between point-source trichloroethene (TCE) plumes and ubiquitous, non-point source pollutants such as nitrate. This study aims to conceptualise critical biogeochemical gradients in the hyporheic zone which govern the export potential of these redox-sensitive pollutants from carbon-poor, oxic aquifers. Within the TCE plume discharge zone, discrete vertical profiling of the upper 100 cm of sediment pore water chemistry revealed an 80% increase in dissolved organic carbon (DOC) concentrations and 20-60 cm thick hypoxic zones (<2 mg O2 L-1) within which most reactive transport was observed. A 33% reduction of nitrate concentrations coincided with elevated pore water nitrous oxide concentrations as well as the appearance of manganese and the TCE metabolite cis-1,2-dichloroethene (cDCE). Elevated groundwater nitrate concentrations (>50 mg L-1) create a large stoichiometric demand for bioavailable DOC in discharging groundwater. With the benefit of a high-resolution grid of pore water samplers investigating the shallowest 30 cm of hypoxic groundwater flow paths, we identified DOC-rich hotspots associated with submerged vegetation (Ranunculus spp.), where low-energy metabolic processes such as mineral dissolution/reduction, methanogenesis and ammonification dominate. Using a chlorine index metric, we show that enhanced TCE to cDCE transformation takes place within these biogeochemical hotspots, highlighting their relevance for natural plume attenuation.

Natural attenuation of chlorinated ethenes in hyporheic zones: A review of key biogeochemical processes and in-situ transformation potential.

Chlorinated ethenes (CEs) are legacy contaminants whose chemical footprint is expected to persist in aquifers around the world for many decades to come. These organohalides have been reported in river systems with concerning prevalence and are thought to be significant chemical stressors in urban water ecosystems. The aquifer-river interface (known as the hyporheic zone) is a critical pathway for CE discharge to surface water bodies in groundwater baseflow. This pore water system may represent a natural bioreactor where anoxic and oxic biotransformation process act in synergy to reduce or even eliminate contaminant fluxes to surface water. Here, we critically review current process understanding of anaerobic CE respiration in the competitive framework of hyporheic zone biogeochemical cycling fuelled by in-situ fermentation of natural organic matter. We conceptualise anoxic-oxic interface development for metabolic and co-metabolic mineralisation by a range of aerobic bacteria with a focus on vinyl chloride degradation pathways. The superimposition of microbial metabolic processes occurring in sediment biofilms and bulk solute transport delivering reactants produces a scale dependence in contaminant transformation rates. Process interpretation is often confounded by the natural geological heterogeneity typical of most riverbed environments. We discuss insights from recent field experience of CE plumes discharging to surface water and present a range of practical monitoring technologies which address this inherent complexity at different spatial scales. Future research must address key dynamics which link supply of limiting reactants, residence times and microbial ecophysiology to better understand the natural attenuation capacity of hyporheic systems.

Nested monitoring approaches to delineate groundwater trichloroethene discharge to a UK lowland stream at multiple spatial scales.

Integrated approaches for the identification of pollutant linkages between aquifers and streams are of crucial importance for evaluating the environmental risks posed by industrial contaminants like trichloroethene (TCE). This study presents a systematic, multi-scale approach to characterising groundwater TCE discharge to a 'gaining' UK lowland stream receiving baseflow from a major Permo-Triassic sandstone aquifer. Beginning with a limited number of initial monitoring points, we aim to provide a 'first pass' mechanistic understanding of the plume's fate at the aquifer/stream interface using a novel combination of streambed diffusion samplers, riparian monitoring wells and drive-point mini-piezometers in a spatially nested sampling configuration. Our results indicate the potential discharge zone of the plume to extend along a stream reach of 120 m in length, delineated by a network of 60 in-situ diffusion samplers. Within this section, a 40 m long sub-reach of higher concentration (>10 µg L(-1)) was identified; centred on a meander bend in the floodplain. 25 multi-level mini-piezometers installed to target this down-scaled reach revealed even higher TCE concentrations (20-40 µg L(-1)), significantly above alluvial groundwater samples (<6 µg L(-1)) from 15 riparian monitoring wells. Significant lateral and vertical spatial heterogeneity in TCE concentrations within the top 1m of the streambed was observed with the decimetre-scale vertical resolution provided by multi-level mini-piezometers. It appears that the distribution of fine-grained material in the Holocene deposits of the riparian floodplain and below the channel is exerting significant local-scale geological controls on the location and magnitude of the TCE discharge. Large-scale in-situ biodegradation of the plume was not evident during the monitoring campaigns. However, detections of cis-1,2-dichloroethene and vinyl chloride in discrete sections of the sediment profile indicate that shallow (e.g., <20 cm) TCE transformation may be significant at a local scale in the streambed deposits. Our findings highlight the need for efficient multi-scale monitoring strategies in geologically heterogeneous lowland stream/aquifer systems in order to more adequately quantify the risk to surface water ecological receptors posed by point-source groundwater contaminants like TCE.