Organic Contaminants In Surface Waters Research Articles

Long-term removal of perfluoroalkyl substances via activated carbon process for general advanced treatment purposes

Granular or powdered activated carbon (GAC/PAC) processes are installed in full-scale drinking water treatment plants (DWTPs) to reduce disinfection byproduct precursors, odor, ammonia, and pesticides. This study investigated the ability of GAC/PAC processes in 23 DWTPs to remove per- and polyfluoroalkyl substances (PFASs). In the GAC process, filter breakthrough of perfluoroalkyl carboxylic acids (PFCAs) occurred faster as the PFCA chain length is decreased. During periods of high water temperatures (20−29 °C), the effluent concentration of two short-chain PFCAs (C4 and C5) surpassed that of the influent after the throughput reached 5,000−7,500 bed volumes (equivalent to 2−3 months) due to desorption. However, such desorption was not observed during periods of low water temperatures (5−19 °C). Meanwhile, long-chain PFCAs were consistently removed, as the GAC was replaced before breakthrough became noticeable. PFAS removal deteriorated at a remarkably fast rate after a partial breakthrough of several tens of percent. Biological activated carbon was proved ineffective in removing PFASs due to its diminished adsorption capacity after long-term use. The PAC process, however, exhibited a slight decrease in PFCA residual (10%) at higher water temperatures (15−30 °C). The PAC dose required for a certain residual ratio was lower with an increase in the hydrophobicity of PFAS; C8-PFCA only required 20 mg/L of PAC for 50% removal, while C4-PFCA required a significantly higher dose of 100−700 mg/L. Consequently, the activated carbon process, which removes organic contaminants in surface water, was inadequate in removing PFASs, particularly those with short chains. Thus, it is recommended that GAC filters be replaced more frequently (within two months) for short-chain PFAS removal. Further, the adsorption performance of PAC must be enhanced.

Passive sampling hydrophilic and hydrophobic bisphenol analogues using hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membrane in surface waters

Bisphenol analogues (BPs) are ubiquitous emerging contaminants in water environments and have wide polarity ranges (1.65 < log Kow < 7.2). Integrated passive sampling strategy rarely contains hydrophilic and hydrophobic organics simultaneously, while the method has good application perspective in monitoring organic contaminants. This work evaluated passive sampling performance for fifteen BPs in a newly developed passive sampler, i.e., hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membrane (HECAM). In the dynamic accumulation experiments, both hydrophilic and hydrophobic BPs (including moderately hydrophilic BPs) well followed first-order kinetic uptake in the HECAMs. The estimated uptake rate constants, elimination rate constants, and equilibrium partition coefficients for BPs ranged from 4.4 L g−1 d−1 to 14.7 L g−1 d−1, 0.22 d−1 to 0.72 d−1, and 3.99 to 4.64, respectively. The kinetic parameters for BPs in HECAM show limited correlations to log Kow values, which the rule differs from traditional passive sampler. In the study of elimination kinetics, three deuterium labeled compounds showed incomplete elimination in HECAM and did not follow first-order isotropic exchange kinetics. Dual sorption mechanisms including both adsorption and partition were found for chemicals in HECAM, which the partitioned part could release to water and the adsorbed part could not easily release to water from HECAM. As a result, performance reference compounds (PRCs) calibration may be inapplicable to HLB sorbent-based passive sampler. The field deployment of HECAM in coastal waters of Guangdong, China resulted in the detection of eleven BPs, which indicated that the waters have been polluted by various BPs. Finally, monitoring strategy of simultaneous passive sampling hydrophobic and hydrophilic organic contaminants in surface waters was recommended.

Photochemical oxidation of phenols and anilines mediated by phenoxyl radicals in aqueous solution

Reactive intermediates formed upon irradiation of chromophoric dissolved organic matter (CDOM) contribute to the degradation of various organic contaminants in surface waters. Besides well-studied “short-lived” photooxidants, such as triplet state CDOM (3CDOM*) or singlet oxygen, CDOM-derived “long-lived” photooxidants (LLPO) have been suggested as key players in the transformation of electron-rich contaminants. LLPO were hypothesized to mainly consist of phenoxyl radicals derived from phenolic moieties in the CDOM. To test this hypothesis and to better characterize LLPO, the transformation kinetics of selected target compounds (phenols and anilines) induced by a suite of electron-poor model phenoxyl radicals was studied in aerated aqueous solution at pH 8. The phenoxyl radicals were generated by photosensitized oxidation of the parent phenols using aromatic ketones as photosensitizers. Under steady-state irradiation, the presence of any of the electron-poor phenols lead to an enhanced abatement of the phenolic target compounds (at an initial concentration of 1.0 × 10−7 M) compared to solutions containing the photosensitizer but no electron-poor phenol. A trend of increasing reactivity with increasing one-electron reduction potential of the electron-poor phenoxyl radical (range: 0.85‒1.12 V vs. standard hydrogen electrode) was observed. Using the excited triplet state of 2-acetonaphthone as a selective oxidant for phenols, it was observed that the reactivity correlated with the concentration of electron-poor phenoxide present in solution. The rates of transformation of anilines induced by the 4-cyanophenoxyl radical were an order of magnitude smaller than for the phenolic target compounds. This was interpreted as a reduction of the radical intermediates back to the parent compound by the superoxide radical anion. Laser flash photolysis measurements confirmed the formation of the 4-cyanophenoxyl radical in solutions containing 2-acetonaphthone and 4-cyanophenol, and yielded values of (2.6 − 5.3) × 108 M−1 s−1 for the second-order rate constant for the reaction of this radical with 2,4,6-trimethylphenol. These and further results indicate that electron-poor model phenoxyl radicals generated through photosensitized oxidation are useful models to understand the photoreactivity of LLPO as part of the CDOM.

Magnetically separable NiFe2O4/Ag3VO4/Ag2VO2PO4 direct Z‐scheme heterostructure with enhanced visible‐light photoactivity

AbstractBACKGROUNDThe occurrence of organic contaminants in surface water has drawn great concern in recent years. The construction of a heterostructure has been shown to improve photoactivity by boosting the separation of photogenerated charge carriers. In this work, magnetically separable NiFe2O4/Ag3VO4/Ag2VO2PO4 (NFO/AVO/AVPO) heterojunction photocatalysts were synthesized via a chemical etching method in ammonia solution of different concentrations, using NFO/AVPO as the source material. The magnetic NFO/AVO/AVPO not only endows magnetic recoverability using an external magnetic field, but also possesses a heterojunction, boosting the separation of photoinduced charges.RESULTSCompared with NFO, AVPO and NFO/AVPO, NFO/AVO/AVPO composites as synthesized show improved visible‐light photoactivities. At the optimum concentration (0.15 mol L−1) of ammonia solution, the NFO/AVO/AVPO shows 8.5 and 10.7 times improved photodegradation efficiency for methylene blue and imidacloprid than that of pristine NFO/AVPO, respectively. Due to the presence of magnetic NiFe2O4, the NFO/AVO/AVPO can be magnetically separated easily from the photoreaction system using a magnet. The improved photoactivity can be attributed to the formation of a direct Z‐scheme heterojunction, which boosts the separation of photoinduced electron–hole pairs.CONCLUSIONThis work not only opens up a new method to fabricate heterojunction photocatalysts, but also paves the way for designing advanced magnetically separable photocatalysts with improved photoactivity. © 2021 Society of Chemical Industry (SCI).

Non-targeted screening of trace organic contaminants in surface waters by a multi-tool approach based on combinatorial analysis of tandem mass spectra and open access databases

Non-targeted screening (NTS) in mass spectrometry (MS) helps alleviate the shortcoming of targeted analysis such as missing the presence of concerning compounds that are not monitored and its lack of retrospective analysis to subsequently look for new contaminants. Most NTS workflows include high resolution tandem mass spectrometry (HRMS2) and structure annotation with libraries which are still limited. However, in silico combinatorial fragmentation tools that simulate MS2 spectra are available to help close the gap of missing compounds in empirical libraries. Three NTS tools were combined and used to detect and identify unknown contaminants at ultra-trace levels in surface waters in real samples in this qualitative study. Two of them were based on combinatorial fragmentation databases, MetFrag and the Similar Partition Searching algorithm (SPS), and the third, the Global Natural Products Social Networking (GNPS), was an ensemble of empirical databases. The three NTS tools were applied to the analysis of real samples from a local river. A total of 253 contaminants were identified by combining all three tools: 209 were assigned a probable structure and 44 were confirmed using reference standards. The two major classes of contaminants observed were pharmaceuticals and consumer product additives. Among the confirmed compounds, octylphenol ethoxylates, denatonium, irbesartan and telmisartan are reported for the first time in surface waters in Canada. The workflow presented in this work uses three highly complementary NTS tools and it is a powerful approach to help identify and strategically select contaminants and their transformation products for subsequent targeted analysis and uncover new trends in surface water contamination.

Endocrine disrupting activities and geochemistry of water resources associated with unconventional oil and gas activity

The rise of hydraulic fracturing and unconventional oil and gas (UOG) exploration in the United States has increased public concerns for water contamination induced from hydraulic fracturing fluids and associated wastewater spills. Herein, we collected surface and groundwater samples across Garfield County, Colorado, a drilling-dense region, and measured endocrine bioactivities, geochemical tracers of UOG wastewater, UOG-related organic contaminants in surface water, and evaluated UOG drilling production (weighted well scores, nearby well count, reported spills) surrounding sites. Elevated antagonist activities for the estrogen, androgen, progesterone, and glucocorticoid receptors were detected in surface water and associated with nearby shale gas well counts and density. The elevated endocrine activities were observed in surface water associated with medium and high UOG production (weighted UOG well score-based groups). These bioactivities were generally not associated with reported spills nearby, and often did not exhibit geochemical profiles associated with UOG wastewater from this region. Our results suggest the potential for releases of low-saline hydraulic fracturing fluids or chemicals used in other aspects of UOG production, similar to the chemistry of the local water, and dissimilar from defined spills of post-injection wastewater. Notably, water collected from certain medium and high UOG production sites exhibited bioactivities well above the levels known to impact the health of aquatic organisms, suggesting that further research to assess potential endocrine activities of UOG operations is warranted.

Source-related smart suspect screening in the aqueous environment: search for tire-derived persistent and mobile trace organic contaminants in surface waters

A variant of suspect screening by liquid chromatography–high-resolution mass spectrometry (LC-HRMS) is proposed in this study: Samples of a potential source of contamination and of an environmental sample close to this source are first analyzed in a non-targeted manner to select source-related suspects and to identify them. The suspect list compiled from such an exercise is then applied to LC-HRMS data of environmental samples to ascribe and to identify persistent and mobile contaminants in the water cycle that may originate from the source under study. This approach was applied to tire crumb rubber (source) and road dust (close to source); by comparison of the two data sets, 88% of the features detected in tire leachate could be excluded. Of the 48 suspects remaining, a total of 41 could be tentatively identified as either related to hexamethoxymethyl melamine or cyclic amines, benzothiazoles, or glycols. Subsequently, environmental samples were searched for these suspects: 85% were determined in an urban creek after a combined sewer overflow and 67% in the influent of a municipal wastewater treatment plant (WWTP). These exceptionally high rates of positive findings prove that this source-related smart suspect screening effectively directs the effort of selecting and identifying unknown contaminants to those related to the source of interest. The WWTP effluent and the urban creek during dry weather also showed the presence of numerous contaminants that may stem from tire and road wear particles (TRWP) in road runoff. Contribution from other sources, however, cannot be ruled out.Graphical abstract

Passive and grab sampling methods to assess pesticide residues in water. A review

There is actually health concern about the uncontrolled use of pesticides, as some banned pesticides continue to be used in many regions of the world, especially in Latin America. Advanced analytical methods are thus required to detect pesticides in water. Common pesticide analysis is done by grab sampling of water volumes ranging from milliliters to liters. Grab sampling is suitable for moderate to high pesticide concentrations, but fails to detect trace levels and shows only a single-time snapshot of pesticide levels. Alternatively, passive sampling extracts and collects water directly in situ, thus allowing time for pollutants to be accumulated into the sampler. Passive sampling has recently become a major tool for extraction of organic contaminants in surface water, groundwater and wastewater. Diverse pollutants have been studied, such as pesticides, illicit and prescription drugs, metals, polycyclic aromatic hydrocarbons and cyanobacterial microcystin toxins. This review describes the main devices of passive sampling, used for the extraction of pesticides in waters.

The promotion effect of phenolic acid compound on the photo-removal of estrogen from water under simulated sunlight irradiation

Phenol and its derivatives have received a great deal of attention due to their ubiquitous existence in surface water and recognized to be the main constituents in humic substance. However, few relevant studies concerned whether and how phenolic acids affect the fate of endocrine disrupting chemicals in surface water. In this study, the effect of 3, 5-dihydroxybenzoic acid (DHBA) on the phototransformation of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) under simulated sunlight were systematically investigated. The results showed that DHBA significantly promoted the photolysis of estrogen mainly by producing triplet-excited state and superoxide anion based on density functional theory calculation and quenching experiments for reactive oxygen species (ROS). Interestingly, the intermediates of DHBA could compete with estrogen for reactive species to reduce the enhancing effect on E2 degradation, indicating that the changes on the structure and functional groups of phenolic compounds in photochemical process could further affect the photolysis of contaminants. Photodegradation pathways of E2 in the presence of DHBA were speculated as hydroxylation, oxidation, and coupling reactions. The study provided new insights for better understanding the effects of phenolic compounds on the natural attenuation of emerging organic contaminants in surface water.

Impact of method parameters on the performance of suspect screening for the identification of trace organic contaminants in surface waters

The performance of a suspect screening method to detect diverse small-molecule trace organic contaminants (TOCs) was systematically evaluated using a set of 39 model compounds. Experiments showed that ionization efficiency, ion transfer parameters, and chromatography could affect the detection of TOCs. As expected, compounds with low ionization yields and poorly retained compounds in chromatographic columns are more difficult to identify in the samples at environmental concentrations. Similarly, TOCs with large deviations from the average mass of the compounds screened were not transmitted efficiently in the mass spectrometer thus negatively affecting their detection. The suspect screening method was validated in terms of recovery and limits of identification of the model compounds using three different types of solid-phase extraction cartridges (reversed phase with polar groups, mixed-mode anion exchange, and mixed mode cation exchange). Experiments showed that more than two-thirds of the model compounds had recoveries &gt;75% with each of the three cartridges, and comparison of limits of identification showed that more than one-half of the model compounds could be identified at concentrations between 6 and 100 ng L−1. However, it was observed that the amount of co-extracted compounds was higher in mixed-mode ion exchangers compared with the reversed-phase cartridge. Application of the suspect screening method using the three different cartridges to surface water samples showed that between 0 to 3% of the positive matches found by the peak identification algorithm were classified as probable structures. Solutions to improve suspect screening of TOCs are proposed and discussed.

Continuous low-level aquatic monitoring (CLAM) samplers for pesticide contaminant screening in urban runoff: Analytical approach and a field test case

Monitoring of surface waters for organic contaminants is costly. Grab water sampling often results in non-detects for organic contaminants due to missing a pulse event or analytical instrumentation limitations with a small sample size. Continuous Low-Level Aquatic Monitoring (CLAM) samplers (C.I.Agent® Solutions) continually extract and concentrate organic contaminants in surface water onto a solid phase extraction disk. Utilizing CLAM samplers, we developed a broad spectrum analytical screen for monitoring organic contaminants in urban runoff. An intermediate polarity solid phase, hydrophobic/lipophilic balance (HLB), was chosen as the sorbent for the CLAM to target a broad range of compounds. Eighteen urban-use pesticides and pesticide degradates were targeted for analysis by LC/MS/MS, with recoveries between 59 and 135% in laboratory studies. In field studies, CLAM samplers were deployed at discrete time points from February 2015 to March 2016. Half of the targeted chemicals were detected with reporting limits up to 90 times lower than routine 1-L grab samples with good precision between field replicates. In a final deployment, CLAM samplers were compared to 1-L water samples. In this side-by-side comparison, imidacloprid, fipronil, and three fipronil degradates were detected by the CLAM sampler but only imidacloprid and fipronil sulfone were detected in the water samples. However, concentrations of fipronil sulfone and imidacloprid were significantly lower with the CLAM and a transient spike of diuron was not detected. Although the CLAM sampler has limitations, it can be a powerful tool for development of more focused and informed monitoring efforts based on pre-identified targets in the field.

Probing the Photosensitizing and Inhibitory Effects of Dissolved Organic Matter by Using N,N-dimethyl-4-cyanoaniline (DMABN).

Dissolved organic matter (DOM) can act as a photosensitizer and an inhibitor in the phototransformation of several nitrogen-containing organic contaminants in surface waters. The present study was performed to select a probe molecule that is suitable to measure these antagonistic properties of DOM. Out of nine studied nitrogen-containing aromatic compounds, 4-cyanoaniline, N,N-dimethyl-4-cyanoaniline (DMABN), sotalol (a β-blocker) and sulfadiazine (a sulfonamide antibiotic) exhibited a marked photosensitized transformation that could be substantially inhibited by addition of phenol as a model antioxidant. The photosensitized transformation of DMABN, the selected probe compound, was characterized in detail under UV-A and visible irradiation (λ > 320 nm) to avoid direct phototransformation. Low reactivity of DMABN with singlet oxygen was found (second-order rate constant <2 × 107 M-1 s-1). Typically at least 85% of the reactivity of DMABN could be inhibited by DOM or the model antioxidant phenol. The photosensitized transformation of DMABN mainly proceeded (>72%) through demethylation yielding N-methyl-4-cyanoaniline and formaldehyde as primary products. In solutions of standard DOM extracts and their mixtures the phototransformation rate constant of DMABN was shown to vary nonlinearly with the DOM concentration. Model equations describing the dependence of such rate constants on DOM and model antioxidant concentrations were successfully used to fit experimental data.

Broad spectrum screening of 463 organic contaminants in rivers in Macedonia

Target screening of 463 organic contaminants in surface water using ultra high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) with direct injection was performed in spring of 2015 in northern Macedonia, at six sampling sites in four rivers belonging to Vardar basin: Kriva, Zletovska, Bregalnica and Vardar. The aim of the study was to differentiate between various types of organic contamination characteristic for different types of anthropogenic activities, such as mining, agriculture, and urbanization. Depending on the studied river, 9–16% of analyzed compounds were detected. The highest total levels of organic contaminants were recorded in agriculturally impacted Bregalnica River (1839–1962ngL−1) and Vardar River downstream from the city of Skopje (1945ngL−1), whereas the lowest level was found in the mining impacted Zletovska River (989ngL−1). The principal organic contaminants of the Bregalnica River were herbicides (45–55% of all detected compounds; 838–1094ngL−1), with the highest concentrations of bentazone (407–530ngL−1) and molinate (84–549ngL−1), common herbicides in rice cultivation. The main organic contaminants in the other rivers were drugs (70–80% of all detected compounds), with antibiotics as a predominant drug class. The highest drug concentrations were measured in the Vardar River, downstream from Skopje (1544ngL−1). Screening of surface water by UHPLC-QTOF-MS was proven as a practical tool for fast collection of comprehensive preliminary information on organic contamination of natural waters, which can present a significant contribution in the monitoring and preservation of good ecological status of freshwater ecosystems.

First comprehensive screening of lipophilic organic contaminants in surface waters of the megacity Jakarta, Indonesia

Jakarta is an Indonesian coastal megacity with over 10 million inhabitants. The rivers flowing through the city receive enormous amounts of untreated wastewaters and discharge their pollutant loads into Jakarta Bay. We utilized a screening approach to identify those site-specific compounds that represent the major contamination of the cities' water resources, and detected a total number of 71 organic contaminants in Jakarta river water samples. Especially contaminants originating from municipal wastewater discharges were detected in high concentrations, including flame retardants, personal care products and pharmaceutical drugs.A flame retardant, a synthetic fragrance and caffeine were used as marker compounds to trace the riverine transport of municipal wastewaters into Jakarta Bay. These markers are also appropriate to trace municipal wastewater discharges to other tropical coastal ecosystems. This application is in particular useful to evaluate wastewater inputs from land-based sources to habitats which are sensitive to changing water quality, like coral reefs.

Co-occurrence of Photochemical and Microbiological Transformation Processes in Open-Water Unit Process Wetlands.

The fate of anthropogenic trace organic contaminants in surface waters can be complex due to the occurrence of multiple parallel and consecutive transformation processes. In this study, the removal of five antiviral drugs (abacavir, acyclovir, emtricitabine, lamivudine and zidovudine) via both bio- and phototransformation processes, was investigated in laboratory microcosm experiments simulating an open-water unit process wetland receiving municipal wastewater effluent. Phototransformation was the main removal mechanism for abacavir, zidovudine, and emtricitabine, with half-lives (t1/2,photo) in wetland water of 1.6, 7.6, and 25 h, respectively. In contrast, removal of acyclovir and lamivudine was mainly attributable to slower microbial processes (t1/2,bio = 74 and 120 h, respectively). Identification of transformation products revealed that bio- and phototransformation reactions took place at different moieties. For abacavir and zidovudine, rapid transformation was attributable to high reactivity of the cyclopropylamine and azido moieties, respectively. Despite substantial differences in kinetics of different antiviral drugs, biotransformation reactions mainly involved oxidation of hydroxyl groups to the corresponding carboxylic acids. Phototransformation rates of parent antiviral drugs and their biotransformation products were similar, indicating that prior exposure to microorganisms (e.g., in a wastewater treatment plant or a vegetated wetland) would not affect the rate of transformation of the part of the molecule susceptible to phototransformation. However, phototransformation strongly affected the rates of biotransformation of the hydroxyl groups, which in some cases resulted in greater persistence of phototransformation products.

Modeling the transport of organic chemicals between polyethylene passive samplers and water in finite and infinite bath conditions.

Understanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels. The authors used the infinite bath model to infer fractional equilibration of PCB and DDT analytes in field-deployed PE, and the results were nearly identical to those obtained using the sampling rate model. However, further comparison of the model and the sampling rate model revealed that the exchange of chemicals was inconsistent with the sampling rate model for partially or fully membrane-controlled transfer, which would be expected in turbulent conditions or when targeting compounds with small polymer diffusivities and small partition coefficients (e.g., phenols, some pesticides, and others). The model can be applied to other polymers besides PE as well as other chemicals and in any transfer regime (membrane, mixed, or water boundary layer-controlled). Lastly, the authors illustrate practical applications of this model such as improving passive sampler design and understanding the kinetics of passive dosing experiments.

Analysis of polar organic contaminants in surface water of the northern Adriatic Sea by solid-phase extraction followed by ultrahigh-pressure liquid chromatography–QTRAP® MS using a hybrid triple-quadrupole linear ion trap instrument

Water-soluble polar organic contaminants are discharged by rivers, cities, and ships into the oceans. Little is known on the fate, pollution effects, and thresholds of toxic chemical mixtures in the marine environment. A new trace analytical method was developed for the multi-compound analysis of polar organic chemical contaminants in marine waters. The method is based on automated solid-phase extraction (SPE) of one-liter water samples followed by ultrahigh-pressure liquid chromatography triple-quadrupole linear ion-trap mass spectrometry (UHPLC-QTRAP(®) MS). Marine water samples from the open Adriatic Sea taken 16km offshore from Venice (Italy) were analyzed. Method limits of quantification (LOQs) in the low picogram per liter (pg/l) concentration range were achieved. Among the 67 target chemicals analyzed, 45 substances could be detected above the LOQ. The chemicals detected at the highest concentrations were caffeine (up to 367ng/l), nitrophenol (36ng/l), 2,4-dinitrophenol (34ng/l), 5-methyl-1H-benzotriazole (18.5ng/l), sucralose (11ng/l), 1H-benzotriazole (9.2ng/l), terbuthylazine (9ng/l), alachlor (7.7ng/l), atrazine-desisopropyl (6.6ng/l), diethyltoluamide (DEET) (5.0ng/l), terbuthylazine-desethyl (4.3ng/l), metolachlor (2.8ng/l), perfluorooctanoic acid (PFOA) (2.5ng/l), perfluoropentanoic acid (PFPeA) (2.3ng/l), linuron (2.3ng/l), perfluorohexanoic acid (PFHxA) (2.2ng/l), diuron (2.0ng/l), perfluorohexane sulfonate (PFHxS) (1.6ng/l), simazine (1.6ng/l), atrazine (1.5ng/l), and perfluorooctane sulfonate (PFOS) (1.3ng/l). Higher concentrations were detected during summer due to increased levels of tourist activity during this period.

Assessing Exposure to Transformation Products of Soil-Applied Organic Contaminants in Surface Water: Comparison of Model Predictions and Field Data

Transformation products (TPs) of chemicals released to soil, for example, pesticides, are regularly detected in surface and groundwater with some TPs even dominating observed pesticide levels. Given the large number of TPs potentially formed in the environment, straightforward prioritization methods based on available data and simple, evaluative models are required to identify TPs with a high aquatic exposure potential. While different such methods exist, none of them has so far been systematically evaluated against field data. Using a dynamic multimedia, multispecies model for TP prioritization, we compared the predicted relative surface water exposure potential of pesticides and their TPs with experimental data for 16 pesticides and 46 TPs measured in a small river draining a Swiss agricultural catchment. Twenty TPs were determined quantitatively using solid-phase extraction liquid chromatography mass spectrometry (SPE-LC-MS/MS), whereas the remaining 26 TPs could only be detected qualitatively because of the lack of analytical reference standards. Accordingly, the two sets of TPs were used for quantitative and qualitative model evaluation, respectively. Quantitative comparison of predicted with measured surface water exposure ratios for 20 pairs of TPs and parent pesticides indicated agreement within a factor of 10, except for chloridazon-desphenyl and chloridazon-methyl-desphenyl. The latter two TPs were found to be present in elevated concentrations during baseflow conditions and in groundwater samples across Switzerland, pointing toward high concentrations in exfiltrating groundwater. A simple leaching relationship was shown to qualitatively agree with the observed baseflow concentrations and to thus be useful in identifying TPs for which the simple prioritization model might underestimate actual surface water concentrations. Application of the model to the 26 qualitatively analyzed TPs showed that most of those TPs categorized as exhibiting a high aquatic exposure potential could be confirmed to be present in the majority of water samples investigated. On the basis of these results, we propose a generally applicable, model-based approach to identify those TPs of soil-applied organic contaminants that exhibit a high aquatic exposure potential to prioritize them for higher-tier, experimental investigations.

Chemical and Toxicologic Assessment of Organic Contaminants in Surface Water Using Passive Samplers

Passive sampling methodologies were used to conduct a chemical and toxicologic assessment of organic contaminants in the surface waters of three geographically distinct agricultural watersheds. A selection of current-use agrochemicals and persistent organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides, were targeted using the polar organic chemical integrative sampler (POCIS) and the semipermeable membrane device passive samplers. In addition to the chemical analysis, the Microtox assay for acute toxicity and the yeast estrogen screen (YES) were conducted as potential assessment tools in combination with the passive samplers. During the spring of 2004, the passive samplers were deployed for 29 to 65 d at Leary Weber Ditch, IN; Morgan Creek, MD; and DR2 Drain, WA. Chemical analysis of the sampler extracts identified the agrochemicals predominantly used in those areas, including atrazine, simazine, acetochlor, and metolachlor. Other chemicals identified included deethylatrazine and deisopropylatrazine, trifluralin, fluoranthene, pyrene, cis- and trans-nonachlor, and pentachloroanisole. Screening using Microtox resulted in no acutely toxic samples. POCIS samples screened by the YES assay failed to elicit a positive estrogenic response.

Inhibitory effect of dissolved organic matter on triplet-induced oxidation of aquatic contaminants

Excited triplet states of organic chromophores, in particular aromatic ketones, are capable of inducing oxidation of a variety of organic compounds. These reactions probably play an important role in the degradation of organic contaminants in sunlit natural waters. The effect of dissolved natural organic matter (DOM) on the oxidation rate of twenty-two aquatic organic contaminants, including phenols, anilines, phenylurea and s-triazine herbicides, and some pharmaceuticals, was investigated using photoexcited benzophenone-4-carboxylate (CBBP) as the oxidant. For about half of the studied compounds, a decrease in depletion rate was observed in the presence of Suwannee River fulvic acid, used as a reference DOM. Also, depletion rates decreased with increasing DOM concentration, as verified for five selected compounds. Such an inhibitory effect of DOM on oxidation is attributed to its antioxidant properties, whereby oxidation intermediates of the contaminants are supposed to be reduced back to their parent compounds. The presented screening study shows that DOM may be a relevant factor for inhibiting the oxidation of many organic contaminants in surface waters and possibly in engineered water treatment systems.