A key success factor for the performance of passive samplers is the proper calibration of sampling rates. Sampling rates for a wide range of polar organic compounds are available for Chemcatchers and polar organic chemical integrative samplers (POCIS), but the mechanistic models that are needed to understand the effects of exposure conditions on sampling rates need improvement. Literature data on atrazine sampling rates by these samplers were reviewed with the aim of assessing what can be learned from literature reports of this well-studied compound and identifying knowledge gaps related to the effects of flow and temperature. The flow dependency of sampling rates could be described by a mass transfer resistance model with 1 (POCIS) or 2 (Chemcatcher) adjustable parameters. Literature data were insufficient to evaluate the temperature effect on the sampling rates. An evaluation of reported sampler configurations showed that standardization of sampler design can be improved: for POCIS with respect to surface area and sorbent mass, and for Chemcatcher with respect to housing design. Several reports on atrazine sampling could not be used because the experimental setups were insufficiently described with respect to flow conditions. Recommendations are made for standardization of sampler layout and documentation of flow conditions in calibration studies. Environ Toxicol Chem 2018;37:1786-1798. © 2018 SETAC.
An index to benchmark pesticide mobility relevant to surface water runoff and soil erosion (surface water mobility index, or SWMI) was derived based on two key environmental fate parameters: degradation half-life and organic carbon-normalized soil/water sorption coefficient (Koc). Values assigned with the index of each individual compound correlate well with the concentration trend of 13 pesticides monitored in six Lake Erie, USA, tributaries from 1983 to 1991. Regression using a power function of SWMI fits concentration data well at various percentiles in the database for each tributary and all six tributaries combined, with r2 ranging from 0.71 to 0.94 for the concentrations at the 95th percentile. Good agreement was also obtained between SWMI and the time-weighted annual mean concentrations (r2 = 0.67-0.87). Although concentrations at or near peaks tend to be driven by rare hydrological events (intense precipitation immediately after application), SWMI explains the peak concentration data generally well (r2 = 0.53-0.86). The SWMI-concentration relationship was further evaluated with two other pesticide monitoring databases: the U.S. Geological Survey National Water Quality Assessment Program White River Study Unit (1991-1996) at Hazelton, Indiana, USA, and the Syngenta (previously Novartis) Voluntary Monitoring Program with Community Water Systems at the Higginsville City Lake, Missouri, USA (1995-1997). The ability of the proposed SWMI to discriminate pesticide runoff mobility and its correlation with surface water monitoring data can be significant in the development of screening methodologies and data-based models for government agencies and/or practitioners in general facing increasing pressure to assess pesticide occurrence in aquatic environments.
The effects of changing hydrodynamic conditions and changing temperatures on polar organic chemical integrative sampler (POCIS) sampling rates (R ) were investigated for 12 crop protection chemicals. Exposure concentration was held constant in each laboratory experiment, and flow velocities were calculated from measured mass transfer coefficients of the water boundary layer near the surface of POCIS devices. At a given temperature R generally increased by a factor of 2 to 5 between a stagnant condition and higher flow velocities (6-21 cm/s), but R for most compounds was essentially constant between the higher flow velocities. When temperature was varied between 8 and 39 °C for a given flow condition, R increased linearly. In general, R increased by a factor of 2 to 4 and 2 to 8 over this temperature range under flow and stagnant conditions, respectively. An Arrhenius model was used to describe the dependence of POCIS sampling rates on temperature. Adjustments of R for temperature did not fully explain observed differences between time-weighted average concentrations of atrazine determined from POCIS and from composite water sampling in a field setting, suggesting that the effects of other competing factors still need to be evaluated. Environ Toxicol Chem 2018;37:2331-2339. © 2018 SETAC.
Field‐based atrazine sampling rates (Rs) obtained by the polar organic chemical integrative sampler (POCIS) method were measured in 9 headwater streams over 3 yr covering 5 to 6 exposure periods of 2 to 3 wk/site/yr. Rates were best in line with the model Rs = 148 mL/d, with a standard deviation of 0.17 log units (factor 1.5). The POCIS canisters reduced mass transfer coefficients of the water boundary layer by a factor of 2 as measured by alabaster dissolution rates. A mechanistic model that accounts for flow and temperature effects yielded a fair estimate of the effective exchange surface area (12.5 ± 0.8 cm2). This model could only be tested for higher flow velocities because of uncertainties associated with the measurement of flow velocities <1 cm/s. Pictures of sorbent distributions in POCIS devices showed that the effective exchange surface area varied with time during the exposures. Error analysis indicated that sorbent distributions and chemical analysis were minor error sources. Our main conclusion is that an atrazine sampling rate of 148 mL/d yielded consistent results for all 3 yr across 9 headwater streams. Environ Toxicol Chem 2020;39:1334–1342. © 2020 SETAC
An enantioselective method for the separation and quantification of the diastereomer pairs of metolachlor and S-metolachlor in surface and ground waters is presented. Samples are purified and concentrated using a C18 (octadecyl silica) solid-phase extraction (SPE) procedure and analyzed by chiral column liquid chromatography-mass spectrometry/mass spectrometry (LC/MS/MS) interfaced with either atmospheric pressure chemical ionization (APcI) or atmospheric pressure photoionization (APPI) sources. The overall mean percent procedural recoveries (percent relative standard deviations) are 89% (10.6%) for surface water and 80% (9.1%) for ground water. The method limit of quantitation (LOQ) is 0.10 ppb. The method validation was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160.
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