Organic Contaminants In Groundwater Research Articles

Characterization of the migration of organic contaminants in laboratory-scale groundwater polluted by underground coal gasification.

Underground coal gasification (UCG) is a promising technology, but the groundwater pollution caused by UCG is a potential risk to the environment. The measured results of the stratum in the combustion cavity resulting from UCG had proven that the combustion cavity would be filled with some UCG residues and caving rocks when UCG was finished. The pollutants in underground water around the combustion cavity include organic pollutants, inorganic pollutants, and ammonia nitrogen, and one of the primary organic pollutants is phenol. The migration and diffusion characteristics of organic pollutants (taking phenol as a representative) in the groundwater of the combustion cavity were investigated by breakthrough experiments and numerical simulations. The results show that the hydraulic conductivity of the coarse UCG residues is much higher than that of fine residues, and the hydraulic conductivity of the UCG residues with the size of - 0.15 mm and 0.15-0.3 mm are 4.68 × 10-6 m/s and 1.91 × 10-4 m/s respectively. The dispersivity λ for the migration of organic pollutants will be influenced significantly by the size of UCG residues in fractures of the combustion cavity, while the distribution coefficient Kd will not. The dispersivity of organic pollutants in the fine UCG residues is more significant than that in the coarse residues, and the λ for the two kinds of residues are 3.868 cm and 1.765 cm, respectively. The shape of the migration path slightly affects the pollutant concentration distribution along the path, but the width of a path has a more pronounced influence on the concentration distribution. In this research, the influence was formulated by a new technical term, MPWIT, which is related to transverse dispersion. Specifically, while the transverse dispersion values account for 20% and 10% of the longitudinal dispersion, respectively, the corresponding MPWIT values are 39.48 mm and 33.96 mm.

Prioritization of organic contaminants in China's groundwater based on national-scale monitoring data and their persistence, bioaccumulation, and toxicity

There has been increasing concern regarding the adverse environmental and health effects of organic pollutants. A list of priority control organic pollutants (PCOPs) can provide regulatory frameworks for the use and monitoring of organic compounds in the environment. In this study, 20,010 groundwater samples were collected from 15 “first level” groundwater resource zones in China. Fifty (50) organic compounds were analyzed based on their prevalence, occurrence, and physicochemical properties (persistence, bioaccumulation, and toxicity). Results showed that 16 PCOPs, including 12 pesticides, 3 aromatic hydrocarbons (AHs), and 1 phthalate ester, were recognized. Pesticides and AHs accounted for 75 % and 18.75 % of the high-priority pollutants, respectively. There were significant differences in PCOPs between confined and phreatic groundwater. Higher concentrations of pesticides were mainly detected in phreatic groundwater. PCOPs detected in samples from the 15 groundwater resource zones were mainly pesticides and AHs. The groundwater data indicate that the organic compounds detected in the Yellow River Basin (YRB), Yangtze River Basin (YZB), Liaohe River Basin (LRB), and Songhua River Basin (SRB) are mainly categorized as Q1 (high priority) and Q2 (medium priority) pollutants based on the contaminants ranking system in China. The findings from this study offer a snapshot of the wide distribution of PCOPs in the surveyed regions, and are expected to establishing treatment and prevention measures at both the regional and national levels in China.

Modeling and optimization study on degradation of organic contaminants using nZVI activated persulfate based on response surface methodology and artificial neural network: a case study of benzene as the model pollutant

Due to the complicated transport and reactive behavior of organic contamination in groundwater, the development of mathematical models to aid field remediation planning and implementation attracts increasing attentions. In this study, the approach coupling response surface methodology (RSM), artificial neural networks (ANN), and kinetic models was implemented to model the degradation effects of nano-zero-valent iron (nZVI) activated persulfate (PS) systems on benzene, a common organic pollutant in groundwater. The proposed model was applied to optimize the process parameters in order to help predict the effects of multiple factors on benzene degradation rate. Meanwhile, the chemical oxidation kinetics was developed based on batch experiments under the optimized reaction conditions to predict the temporal degradation of benzene. The results indicated that benzene (0.25 mmol) would be theoretically completely oxidized in 1.45 mM PS with the PS/nZVI molar ratio of 4:1 at pH 3.9°C and 21.9 C. The RSM model predicted well the effects of the four factors on benzene degradation rate (R2 = 0.948), and the ANN with a hidden layer structure of [8-8] performed better compared to the RSM (R2 = 0.980). In addition, the involved benzene degradation systems fit well with the Type-2 and Type-3 pseudo-second order (PSO) kinetic models with R2 > 0.999. It suggested that the proposed statistical and kinetic-based modeling approach is promising support for predicting the chemical oxidation performance of organic contaminants in groundwater under the influence of multiple factors.

Characterization of DNAPL source zones in clay-sand media via joint inversion of DC resistivity, induced polarization and borehole data

Toxic organic contaminants in groundwater are pervasive at many industrial sites worldwide. These contaminants, such as chlorinated solvents, often appear as dense non-aqueous phase liquids (DNAPLs). To design efficient remediation strategies, detailed characterization of DNAPL Source Zone Architecture (SZA) is required. Since invasive borehole-based investigations suffer from limited spatial coverage, a non-intrusive geophysical method, direct current (DC) resistivity, has been applied to image the DNAPL distribution; however, in clay-sand environments, the ability of DC resistivity for DNAPLs imaging is limited since it cannot separate between DNAPLs and surrounding clay-sand soils. Moreover, the simplified parameterization of conventional inversion approaches cannot preserve physically realistic patterns of SZAs, and tends to smooth out any sharp spatial variations. In this paper, the induced polarization (IP) technique is combined with DC resistivity (DCIP) to provide plausible DNAPL characterization in clay-sand environments. Using petrophysical models, the DCIP data is utilized to provide tomograms of the DNAPL saturation (SN) and hydraulic conductivity (K). The DCIP-estimated K/SN tomograms are then integrated with borehole measurements in a deep learning-based joint inversion framework to accurately parameterize the highly irregular SZA and provide a refined DNAPL image. To evaluate the performance of the proposed approach, we conducted numerical experiments in a heterogeneous clay-sand aquifer with a complex SZA. Results demonstrate the standalone DC resistivity method fails to infer the DNAPL in complex clay-sand environments. In contrast, the combined DCIP technique provides the necessary information to reconstruct the large-scale features of K/SN fields, while integrating DCIP data with sparse but accurate borehole data results in a high resolution characterization of the SZA.

Understanding the process in the removal of dimethylarsenic by a zirconium-based nanoparticle

Organic arsenic contamination in groundwater and surface water is one of threats to human beings. In this study, a novel zirconium-based nanoparticle was developed to remove dimethylarenic acid (DMA) from aqueous solution. The adsorption behavior was evaluated by various batch adsorption experiments. The pH effect study revealed that the maximum adsorption was achieved around pH 3.0. The ionic strength did not have significant effect on the uptake of DMA. The adsorption kinetics study showed that the adsorption equilibrium was established within 24 h; an intraparticle kinetics model fit the experimental data well. In the adsorption isotherm study, the Langmuir equation described the adsorption data better than the Freundlich equation; the maximum adsorption capacity of the sorbent was calculated to be 58.82 mg-As/g at the optimal pH. In the natural organic matters and coexisting anions effect studies, the presence of humic acid and coexisting anions have little effect on the uptake of DMA. The performance of the Zr-based NP was not largely inhibited in the presence of NOMs and coexisting anion. The FTIR and XPS spectroscopic analyses demonstrated that DMA was successfully adsorbed onto the sorbent and the adsorption mechanism was proposed to be ions exchange between arsenic and sulfate ions.

Presence and Dispersion of Organic and Inorganic Contaminants in Groundwater

This paper offers an extensive examination of studies published in the recent past and highlights the documented issues surrounding groundwater pollution, its sources, and distribution worldwide. The depletion of groundwater resources and the deteriorating overall quality present a significant cause for concern, particularly as a large human population relies on groundwater as a drinking water source. The review focuses on various factors contributing to groundwater pollution, including anthropogenic activities, hydro climatological influences, and natural processes. Special attention is given to organic contaminants such as pesticides, herbicides, and emerging pollutants, which have been found to have a substantial impact on groundwater quality. Additionally, the review covers pollution caused by inorganic pollutants like arsenic and other heavy metals, with a particular emphasis on regions experiencing a higher incidence of these contaminants in groundwater. Furthermore, the paper includes a compilation of studies that highlight the increased occurrence of waterborne illnesses resulting from fecal and microbial contamination, often caused by inadequate sanitary practices. To provide a comprehensive understanding of the global groundwater pollution problem, the review also encompasses an examination of contaminants like fluoride and nitrate.

Distribution, source identification, and health risk of emerging organic contaminants in groundwater of Xiong'an New Area, Northern China

Groundwater contamination in China has been greatly concerned due to dramatically increasing fresh water demand accompanied by economic development. However, little is known about aquifer vulnerability to hazardous matters especially in previously contaminated site of rapidly urbanizing cities. Here, we collected 90 groundwater samples from Xiong'an New Area during wet and dry seasons of 2019 and characterized the composition and distribution of emerging organic contaminants (EOCs) in this strategically developing city. A total of 89 EOCs, assigned to organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and volatile organic compounds (VOCs), were detected with the frequencies ranging from 1.11 %–85.6 %. Methyl tert-butyl ether (16.3 μg/L), Epoxid A (6.15 μg/L), and α-Lindane (5.15 μg/L) could be identified as major contributors to groundwater organic pollution. Significant aggregation of groundwater EOCs along Tang River were found due to historical residue and accumulation from wastewater storage there before 2017. Significant seasonal variations (p < 0.05) in the types and concentrations of EOCs could be attributed to discrepant pollution sources between varying seasons. Human health effects from exposure to groundwater EOCs were further evaluated with negligible risk (<10−4) in most samples (97.8 %) and notable risk (10−6–10−4) in several monitored wells (2.20 %) located along Tanghe Sewage Reservoir. This study provides new evidences for aquifer vulnerability to hazardous matters in historically contaminated sites and is of significant to groundwater pollution controlling and drinking water safety for rapidly urbanizing cities.

Bioenhanced degradation of toluene by layer-by-layer self-assembled silica-based bio-microcapsules.

In this study, micron-sized monodisperse SiO2 microspheres were used as sacrificial templates, and chitosan/polylactic acid (CTS/PLA) bio-microcapsules were produced using the layer-by-layer (LBL) assembly method. Microcapsules isolate bacteria from their surroundings, forming a separate microenvironment and greatly improving microorganisms' ability to adapt to adverse environmental conditions. Morphology observation indicated that the pie-shaped bio-microcapsules with a certain thickness could be successfully prepared through LBL assembly method. Surface analysis showed that the LBL bio-microcapsules (LBMs) had large fractions of mesoporous. The biodegradation experiments of toluene and the determination of toluene degrading enzyme activity were also carried out under external adverse environmental conditions (i.e., unsuitable initial concentrations of toluene, pH, temperature, and salinity). The results showed that the removal rate of toluene by LBMs can basically reach more than 90% in 2 days under adverse environmental conditions, which is significantly higher than that of free bacteria. In particular, the removal rate of toluene by LBMs can reach four times that of free bacteria at pH 3, which indicates that LBMs maintain a high level of operational stability for toluene degradation. Flow cytometry analysis showed that LBL microcapsules could effectively reduce the death rate of the bacteria. The results of the enzyme activity assay showed that the enzyme activity was significantly stronger in the LBMs system than in the free bacteria system under the same unfavorable external environmental conditions. In conclusion, the LBMs were more adaptable to the uncertain external environment, which provided a feasible bioremediation strategy for the treatment of organic contaminants in actual groundwater.

New insight into the activation mechanism of hydrogen peroxide by greigite (Fe3S4) for benzene removal: The combined action of dissolved and surface bounded ferrous iron

Iron sulfides have attracted growing concern in heterogeneous Fenton reaction. However, the structure of iron sulfides is different from that of iron oxides and how the structures affect the activation property of hydrogen peroxide (H2O2) remains unclear. This study investigated benzene removal through the activation of H2O2 by the synthesized magnetite (Fe3O4) and greigite (Fe3S4). The structures of Fe3O4 and Fe3S4 were characterized by XRD and EPR, the electron transfer properties of Fe3O4 and Fe3S4 were analyzed by electrochemical workstation, XPS and DFT. It is revealed that the effective benzene removal rate of 88.86％ in the Fe3S4/H2O2 was achieved, which compared to 15.58％ obtainable from the Fe3O4/H2O2, with the apparent rate constant in the Fe3S4/H2O2 being approximately 65 times over that in the Fe3O4/H2O2. The better H2O2 activation by Fe3S4 was attributed to the significant roles of S (-II) and S vacancies in regulating the dissolution of ferrous iron ions, thus generating abundant free •OH radical. In addition, surface bounded ferrous iron of Fe3S4 could transfer more electrons to H2O2 and O2 to generate more surface bounded •OH and •O2−. This study revealed the combined action of dissolved and surface bounded ferrous iron of greigite on H2O2 activation, and provides an efficient heterogeneous H2O2 activator for the remediation of organic contaminants in groundwater.

Facile Pyrolysis Treatment for the Synthesis of Single-Atom Mn Catalysts Derived from a Hyperaccumulator

Advanced oxidation processes (AOPs) have revealed wide prospects in the application of the degradation of organic contaminants in ground water and soil. High-performance, environmentally friendly, and low-cost single-atom catalysts (SACs) are promising approaches to active persulfate in AOPs. However, the practical application of SACs is restricted by high preparation costs and tedious procedures. Herein, a manganese (Mn) hyperaccumulator, Phytolacca americana, was successfully exploited as a precursor to synthesize a novel Mn SAC (SPBC-700N) via a one-step pyrolysis method. In SPBC-700N, Mn atoms are dispersed atomically upon the carbon matrix and coordinate with four N atoms to form Mn–N4 active sites, which exhibits an extraordinary catalytic activity for peroxymonosulfate (PMS) activation. A large number of reactive oxygen species are formed during the reaction, and over 90% of the antibiotic (chloroquine phosphate/CQP) could be removed within 30 min. The superior catalytic performance of the Mn SAC/PMS system for CQP degradation is ascribed to the synergistic effect of the maximized utilization of Mn atoms and the neighboring pyrrolic N sites, as identified by X-ray absorption fine structure spectroscopy and density function theory calculations. This work not only provides a green and low-cost strategy for synthesizing SACs but also gives an atomic-level insight into the catalytic activity of the Mn–N4 sites for PMS activation.

Impacts of Contaminants on Groundwater Quality in Rukpokwu, Delta Region of Nigeria

This study investigated the characterization of borehole sediment and the impact of contaminants on groundwater quality in the Rukpokwu Community in the delta of Nigeria. The investigation supported by spatial data supported by GIS techniques provides a data baseline for the monitoring of organo-contaminants in groundwater quality in Rukpokwu. This low pH of the groundwater and irritation of the throat and mouth became a concern to the residents. This study is necessary because of the limited data on the level of organic contamination in groundwater in this section of the delta of Niger in Nigeria. So, there was a need to track the source of contamination in this part of the delta of Niger in Nigeria. These previous studies have suggested a highly permeable open aquifer in similar deltaic terrain. Ten (10) samples of borehole sediment and water collected at 30 m depth were being analyzed for textural and physicochemical characteristics. The parameters analyzed include Iron (Fe), Total Petroleum Hydrocarbon &Total Hydrocarbon Content (i.e., TPH and THC respectively) of borehole sediment in association with groundwater quality. Ten (10) sediment samples collected at a depth of 30m and were being analyzed for mean, sorting, skewness and kurtosis, using standard laboratory procedures. Coarse silt, poorly sorted and negatively skewed were the characteristics of the borehole silt. The Kurtosis suggested the leptokurtic and platykurtic nature of the sediment. The TPH and THC range from 0.58 to 0.85 mg/L and 1.26 to 2.84 mg/L respectively. The Fe and pH range in the sediment were 0.85 to 2.46 mg/L and 4.43 to 6.02 respectively. However, Fe in the groundwater ranges from 0.12 to 0.21 mg/L. The results were above the World Health Organization's acceptable contaminant level. Based on the piece of evidence provided by spatial data mapping and textural parameters, the characteristics of the borehole sediment significantly controlled the ingress of contaminants into the groundwater. The source of groundwater contamination is the abnormal concentrations of organic contaminants. These results significantly impact human health in the food chain. This study provides information to the environmental agency for a clean-up process.

A novel thermosensitive persulfate controlled-release hydrogel based on agarose/silica composite for sustained nitrobenzene degradation from groundwater

The increasing risk of organic contamination of groundwater poses a serious threat to the environment and human health, causing an urgent need to develop long-lasting and adaptable remediation materials. Controlled-release materials (CRMs) are capable of encapsulating oxidants to achieve long-lasting release properties in aquifers and considered to be effective strategies in groundwater remediation. In this study, novel hydrogels (ASGs) with thermosensitive properties were prepared based on agarose and silica to achieve controlled persulfate (PS) release. By adjusting the composition ratio, the gelation time and internal pore structure of the hydrogels were regulated for groundwater application, which in turn affected the PS encapsulated amount and release properties. The hydrogels exhibited significant temperature responsiveness, with 6.8 times faster gelation rates and 2.8 times longer controlled release ability at 10 ℃ than at 30 ℃. The ASGs were further combined with zero-valent iron to achieve long-lasting degradation of the typical nitrobenzene compound 2,4-dinitrotoluene (2,4-DNT), and the degradation performance was maintained at 50 % within 14 PV, which was significantly improved compared with that of the PS/ZVI system. This study provided new concepts for the design of controlled-release materials and theoretical support for the remediation of organic contamination.

Contaminant characterization at pesticide production sites in the Yangtze River Delta: Residue, distribution, and environmental risk

The Yangtze River Delta (YRD) is the largest pesticide-producing region in the world. Contamination of pesticide production sites has always been a focus of public attention. Twenty pesticide production sites in YRD were selected to analyze the residue, distribution, and environmental risk of organic contaminants in soil and groundwater. A total of 194 organic chemicals were detected in all soil and groundwater samples from the 20 sites. Eighty-eight constituents of concern (COCs) exceeded the comparison values of Regional Screening Levels (RSLs), and 80 % exceeded the RSLs by more than five times. The toxic effects of COCs in soil and groundwater were dominated by the carcinogenic risk, referred as “non-threshold”. Benzene toluene ethylbenzene & xylene (BTEX) and chloroaliphatic hydrocarbons (CAHs) were the most prevalent at pesticide sites in YRD rather than pesticides, followed by chlorobenzene, chlorophenols, and polycyclic aromatic hydrocarbons (PAHs). CAHs and BTEX could penetrate up to 24 m, while the others were primarily limited to 12 m. Most pesticide production sites showed a great contamination depth of >8 m, some even deeper than 20 m, posing a great risk of contamination to the confined aquifer. Due to the close interconnection of soil with water bodies, the shallow groundwater and adjacent surface water resources are also susceptible to suffering from environmental risk. More than half of the pesticide production sites in the YRD consist primarily of low-permeable clay layers, making in-situ contamination remediation difficult. This study provides a basis for developing remediation technology for pesticide sites in YRD and an ecological reference for further cleaning production and green manufacturing in the pesticide industry.

Control of organic contaminants in groundwater by passive sampling and multivariate statistical analysis

Organic contaminants in groundwater are among the most challenging chemical compound contaminants today, particularly when it comes to understanding their occurrence, origin, and relations in groundwater, as well as the transport processes, fate, and environmental impacts involved. This paper presents the use of active carbon fibre (AFC) passive sampling and multivariate statistical processing of the results to predict the possible occurrence of organic compounds (OCs) in groundwater and to determine the origin of various anthropogenic activity. This study aims to deepen our knowledge on the control of OCs in groundwater by introducing a multi-analytical and multi-elemental holistic approach, using the Dravsko polje aquifer, the largest intergranular aquifer in Slovenia, as an example. The occurrence of OCs in groundwater was determined by means of ACFs and compared against the characteristics of the recharge area and the type of compounds detected. We combined hierarchical cluster analysis (HCA) and principal component analysis (PCA) to identify the relationship between different OCs in groundwater. The relationships between their occurrence, environmental setting and type of compound were determined using multiple linear regression (MLR). From the total of 343 organic compounds detected using passive sampling, 47 were included in further statistical analysis. MLR shows that the environmental setting is one of the most important factors affecting the different types of pollutants in groundwater. MLR models were calculated for different sources of pollution (agricultural, urban, and industrial) based on the environmental setting, land use, agglomeration, infrastructure networks, and hydrogeological characteristics of the aquifer. By means of HCA and PCA, we identified the relationships between different OCs in groundwater. As expected, the strongest correlations were found between primary compounds and their degradation products (e.g. atrazine and desethylatrazine) and compounds of similar use (e.g. atrazine and propazine, also desethylatrazine and propazine, atrazine and simazine). Some of them were also found to have a similar molecular structure (e.g. palmitic and stearic acid, 5-methoxygramine and 5-methoxytryptamine). The use of the same substances in different environments (agricultural/urban) makes them markers of both (different) origins. Therefore, it is particularly important to determine the combination of markers of different origin using multivariate statistical methods, especially in the case of mixed land use. This study identifies the main factors influencing the distribution of groundwater OCs and thus contributes to a more comprehensive understanding of the vulnerability of shallow groundwater to surface-derived contamination in similar environments.

Hydrothermally assisted synthesis of nano zero-valent iron encapsulated in biomass-derived carbon for peroxymonosulfate activation: The performance and mechanisms for efficient degradation of monochlorobenzene

A facile, green and easily-scalable method of synthesizing stable and effective nano zero-valent iron (nZVI)‑carbon composites for peroxymonosulfate (PMS) activation was highly desirable for in-situ groundwater remediation. This study developed a two-step hydrothermally assisted carbothermal reduction method to prepare nZVI-encapsulated carbon composite (Fe@C) using rice straw and ferric nitrate as precursors. The hydrothermal reactions were conducive to iron loading, and carbothermal temperature was crucial for the aromatization and graphitization of hydrothermal carbonaceous products, the reductive transformation of iron oxides into nZVI and the development of porous structure in composites. At carbothermal temperature of 800 °C following hydrothermal reactions, the stable Fe@C800 with nZVI encapsulated in the spherical carbon shell was obtained and exhibited the best catalytic performance for PMS activation and the degradation of monochlorobenzene (MCB) in a wide range of pH values (3−11) with removal efficiency after 120 min reaction and first-order kinetic rate constant (k1) of 98.7% and 0.087 min−1 respectively under the optimum conditions of 10 mM PMS and 0.2 g·L−1 Fe@C800. The inhibiting effects of common co-existed anions (i.e., Cl−, HCO3− and H2PO4−) and humic acid in groundwater on the removal of MCB in Fe@C800/PMS system was also investigated. Both OH-dominated radical processes and nonradical pathways involving 1O2 and surface electron transfers were accounted for PMS activation and MCB removal. The inner nZVI was protected by the carbon shell, endowing Fe@C800 with high reactivity and good reusability. Additionally, 81.2% and 73.5% of MCB removal rates were achieved in tap water and actual contaminated groundwater respectively. This study not only provided a novel strategy to synthesize highly effective and stable nZVI‑carbon composites using the agricultural biomass waste for PMS induced oxidation of organic contaminants in groundwater, but also enhanced the understanding on the activation mechanism of iron‑carbon based catalysts towards PMS.

Electrochemical reductive remediation of trichloroethylene contaminated groundwater using biomimetic iron-nitrogen-doped carbon

Electrochemical dechlorination is a prospective strategy to remediate trichloroethylene (TCE)-contaminated groundwater. In this work, iron-nitrogen-doped carbon (FeNC) mimicking microbiological dechlorination coenzymes was developed for TCE removal under environmentally related conditions. The biomimetic FeNC-900, FeNC-1000, and FeNC-1100 materials were synthesized via pyrolysis at different temperatures (900, 1000, and 1100 °C). Due to the synergistic effect of Fe–N4 active sites and graphitic N sites, FeNC-1000 had the highest electron transfer efficiency and the largest electrochemical active surface area among the as-synthesized FeNC catalysts. The pseudo-first-order rate constants for TCE reduction using FeNC-1000 catalyst are 0.19, 0.28 and 0.36 h−1 at potentials of −0.8 V, −1.0 V and −1.2 V, respectively. Active hydrogen and direct electrons transfer both contribute to the dechlorination from TCE to C2H4 and C2H6. FeNC maintain a high reactivity after five reuse cycles. Our study provides a novel approach for the dechlorination of chlorinated organic contaminants in groundwater.

Assessment of a wide array of contaminants of emerging concern in a Mediterranean water basin (Guadalhorce river, Spain): Motivations for an improvement of water management and pollutants surveillance

This study investigates the occurrence and distribution of 185 organic contaminants (regulated pollutants and contaminants of emerging concern; CECs) in surface and groundwater of the Guadalhorce River basin (southern Spain) providing the most detailed dataset regarding organic pollution presented so far in this area. Up to 63 contaminants were detected in a monitoring campaign conducted in March 2016. Most contaminants were detected more frequently in surface water where they generally present higher concentrations suggesting the prevalence of wastewater discharges into streams as the main pollutant sources. In general, hydrophobic CECs presented the highest frequencies of detection and concentrations, which can be a consequence of several factors: (1) hydrophobic compounds show a higher retardation factor, which result, along with a continuous contaminant input, in a widespread and homogeneous distribution. In contrast, hydrophilic contaminants are more easily transported by water flows towards the lower basin and potentially accumulate as driven by groundwater flow and because of low renewal rates in the detrital aquifers caused by re-pumping and irrigation return flows in agricultural lands; (2) hydrophobic CECs studied in this research are mainly personal care products and organophosphate esters flame retardants and plasticizers, which are present in many different products and are used in large amounts; Also, (3) use of biosolids (reclaimed sewer sludge) as fertilizer for crops is potentially an additional diffuse source of organic pollutants in the study area contributing to a widespread distribution, especially for hydrophobic compounds. Obtained results highlight the need to better define the potential risk of non-regulated contaminants in water resources as well as the great impact of untreated wastewater discharges.

Emerging organic contaminants in shallow groundwater underlying two contrasting peri-urban areas in Uganda.

This study investigated the occurrence and seasonal variation in concentrations of emerging organic contaminants (EOCs) in shallow groundwater underlying two peri-urban areas of Bwaise (highly urbanised) and Wobulenzi (moderately urbanised) in Uganda. Twenty-six antibiotics, 20 hydrocarbons, including 16 polycyclic aromatic hydrocarbons (PAHs), and 59 pesticides were investigated. Ampicillin and benzylpenicillin were the most frequently detected antibiotics in both areas, although at low concentrations to cause direct harm to human health, but could lead to a proliferation of antibiotic resistance genes. The most frequently detected hydrocarbons in Bwaise were naphthalene and xylene while anthracene and fluoranthene were the most frequent in Wobulenzi, also at low concentrations for ecological impact at long-term exposure. Molecular diagnostic ratios indicated pyrogenic and pyrolytic sources of PAHs in both areas. Cypermethrin (for vermin control) was the most frequent pesticide in Bwaise while metalaxyl (attributed to agriculture) was the most frequent in Wobulenzi. Banned organochlorines (8) were also detected in both areas in low concentrations. The pesticide concentrations between the two areas significantly differed (Z = - 3.558; p < 0.01), attributed to contrasting land-use characteristics. In Wobulenzi (wet season), the total pesticide concentrations at all the locations exceeded the European Community parametric guideline value while 75% of the detected compounds exceeded the individual pesticide guideline value. Thus, the antibiotic and pesticide residues in shallow groundwater underlying both Bwaise and Wobulenzi pose potential adverse ecological effects at long-term exposure. Monitoring of EOCs in both highly and moderately urbanised catchments should be strengthened towards mitigating associated risks.

Magnitude of Diffusion- and Transverse Dispersion-Induced Isotope Fractionation of Organic Compounds in Aqueous Systems

Determining whether aqueous diffusion and dispersion lead to significant isotope fractionation is important for interpreting the isotope ratios of organic contaminants in groundwater. We performed diffusion experiments with modified Stokes diaphragm cells and transverse-dispersion experiments in quasi-two-dimensional flow-through sediment tank systems to explore isotope fractionation for benzene, toluene, ethylbenzene, 2,6-dichlorobenzamide, and metolachlor at natural isotopic abundance. We observed very small to negligible diffusion- and transverse-dispersion-induced isotope enrichment factors (ε < −0.4 ‰), with changes in carbon and nitrogen isotope values within ±0.5‰ and ±1‰, respectively. Isotope effects of diffusion did not show a clear correlation with isotopologue mass with calculated power-law exponents β close to zero (0.007 < β < 0.1). In comparison to ions, noble gases, and labeled compounds, three aspects stand out. (i) If a mass dependence is derived from collision theory, then isotopologue masses of polyatomic molecules would be affected by isotopes of multiple elements resulting in very small expected effects. (ii) However, collisions do not necessarily lead to translational movement but can excite molecular vibrations or rotations minimizing the mass dependence. (iii) Solute–solvent interactions like H-bonds can further minimize the effect of collisions. Modeling scenarios showed that an inadequate model choice, or erroneous choice of β, can greatly overestimate the isotope fractionation by diffusion and, consequently, transverse dispersion. In contrast, available data for chlorinated solvent and gasoline contaminants at natural isotopic abundance suggest that in field scenarios, a potential additional uncertainty from aqueous diffusion or dispersion would add to current instrumental uncertainties on carbon or nitrogen isotope values (±1‰) with an additional ±1‰ at most.

Effects of endogenous and exogenous dissolved organic matter on sorption behaviors of bisphenol A onto soils

The transport of organic contaminants in groundwater might be greatly affected by coexistence of dissolved organic matter (DOM) from different sources. In this study, the effects of endogenous and exogenous DOMs (referred to as DOMen and DOMex, respectively) on sorption behavior of bisphenol A (BPA) onto two reference soils were investigated by batch experiments and microscopic characterization. The results showed that BPA sorption onto soils was dominated by soil organic matter content and affected by DOM properties. The effect of DOMen on BPA sorption was also related to the inorganic components of the two soils. The decrease of organic matter content reduced the sorption capacity of fluvo-aquic soil. However, because the content of available inorganic components in black soil was high, after removing DOMen, more inorganic sites were exposed to increase the sorption capacity. In addition, DOMen could form complexes with BPA in solution, thus the removal of DOMen promoted BPA sorption onto black soil. Under the experimental conditions, contribution of DOMex to the total sorption of BPA onto both soils was not more than 30%. Results of dialysis experiments and soil sorption experiments indicated that effects of coexisting DOMex on BPA sorption was related to the affinity of DOMex to soils and complexation of BPA and DOMex. Since the affinity of DOMex to fluvo-aquic soil was relatively low, the complex of BPA and DOMex in solution was the main inhibition mechanism for BPA sorption. For black soil, higher complexation proportion of BPA with DOMex adsorbed onto soil which promoted BPA sorption onto soil. The findings are of significance for understanding the co-migration of DOM with BPA through soils.