Dominique S. O'Brien

Determination of deployment specific chemical uptake rates for SDB-RPD Empore disk using a passive flow monitor (PFM).

The use of the adsorbent styrenedivinylbenzene-reverse phase sulfonated (SDB-RPD) Empore disk in a chemcatcher type passive sampler is routinely applied in Australia when monitoring herbicides in aquatic environments. One key challenge in the use of passive samplers is mitigating the potentially confounding effects of varying flow conditions on chemical uptake by the passive sampler. Performance reference compounds (PRCs) may be applied to correct sampling rates (R(s)) for site specific changed in flow and temperature however evidence suggests the use of PRCs is unreliable when applied to adsorbent passive samplers. The use of the passive flow monitor (PFM) has been introduced for the assessment of site-specific changes in water flow. In the presented study we have demonstrated that the R(s) at which both atrazine and prometryn are accumulated within the SDB-RPD-Empore disk is dependent on the flow conditions. Further, the calibration of the measured R(s) for chemical uptake by the SDB-RPD-Empore disk to the mass lost from the PFM has shown that the PFM provides an accurate measure of R(s) for flow velocities from 0 to 16cms(-1). Notably, for flow rates >16cms(-1), a non linear increase in the R(s) of both herbicides was observed which indicates that the key resistance to uptake into the SDB-RPD Empore disk is associated with the diffusion through the overlying diffusion limiting membrane. Overall the greatest uncertainty remains at very low flow conditions, which are unlikely to often occur in surface waters. Validation of the PFM use has also been undertaken in a limited field study.

Method for the in Situ Calibration of a Passive Phosphate Sampler in Estuarine and Marine Waters

Passive samplers for phosphate were calibrated in the laboratory over a range of flow velocities (0-27 cm s(-1)) and ionic strengths (0-0.62 mol kg(-1)). The observed sampling rates were between 0.006 and 0.20 L d(-1). An empirical model allowed the estimation of these sampling rates with a precision of 8.5%. Passive flow monitors (PFMs), based on gypsum dissolution rates, were calibrated for the same range of flow velocities and ionic strength. Mass loss rates of the PFMs increased with increasing ionic strength. We demonstrate that this increase is quantitatively accounted for by the increased gypsum solubility at higher ionic strengths. We provide a calculation scheme for these solubilities for an environmentally relevant range of temperatures and salinities. The results imply that co-deployed PFMs can be used for estimating the flow effect on the in situ sampling rates of the phosphate samplers, and we expect that the same may hold for other passive samplers.

Determination of deployment specific chemical uptake rates for SPMD and PDMS using a passive flow monitor

Passive sampling techniques facilitate the time-integrated measurement of pollutant concentrations through the use of a selective receiving phase. Accurate quantification using passive sampling devices rely on the implementation of methods that will negate the effects of environmental factors (flow, temperature, etc.) or that will allow the calculation of the chemical specific rates of uptake (R(s)) into the passive sampler employed. We have applied an in situ calibration technique based on the dissolution of gypsum to measure the average water velocity to which a sampler has been exposed. We demonstrate that the loss of gypsum from the passive flow monitor (PFM) can be applied to predict changes in R(s) dependent on flow when using the absorbent SPMD (semipermeable membrane device) and PDMS (polydimethyl siloxan) passive samplers. The application of the PFM will enhance the accuracy of measurements made when calculating and reporting environmental pollutant concentrations using a passive sampling device.

Passive sampling of perfluorinated chemicals in water: In-situ calibration

Perfluorinated chemicals (PFCs) have been recognised as environmental pollutants that require monitoring. A modified polar organic chemical integrative sampler (POCIS) is able to quantify aqueous PFCs. However, with varying external water velocity, PFC sampling rates (Rs) may change, affecting accuracy of derived water concentrations. To facilitate field deployment of this sampler, two methods of in-situ calibration were investigated: performance reference compounds (PRCs) and passive flow monitors (PFMs). Increased Rss (by factors of 1.2-1.9) with PFM loss rate (g d(-1)) were observed for some PFCs. Results indicate PFMs can be used to correct PFC specific Rss for more reliable estimates of environmental concentrations with a precision of about 0.01 L d(-1). Empirical models presented provide an improved means for aquatic monitoring of PFCs. The PRC approach was unsuccessful, confirming concern as to its applicability with such samplers.

A New Method to Quantify the Application Thickness of Sunscreen on Skin

Proper application of sunscreen is essential as an effective public health strategy for skin cancer prevention. Insufficient application is common among sunbathers, results in decreased sun protection and may therefore lead to increased UV damage of the skin. However, no objective measure of sunscreen application thickness (SAT) is currently available for field‐based use. We present a method to detect SAT on human skin for determining the amount of sunscreen applied and thus enabling comparisons to manufacturer recommendations. Using a skin swabbing method and subsequent spectrophotometric analysis, we were able to determine SAT on human skin. A swabbing method was used to derive SAT on skin (in mg sunscreen per cm2 of skin area) through the concentration–absorption relationship of sunscreen determined in laboratory experiments. Analysis differentiated SATs between 0.25 and 4 mg cm−2 and showed a small but significant decrease in concentration over time postapplication. A field study was performed, in which the heterogeneity of sunscreen application could be investigated. The proposed method is a low cost, noninvasive method for the determination of SAT on skin and it can be used as a valid tool in field‐ and population‐based studies.

Understanding the uncertainty of estimating herbicide and nutrient mass loads in a flood event with guidance on estimator selection

The aim of this study was to understand the uncertainty of estimating loads for observed herbicides and nutrients during a flood event and provide guidance on estimator selection. A high-resolution grab sampling campaign (258 samples over 100 h) was conducted during a flood event in a tropical waterway in Queensland, Australia. Ten herbicides and three nutrient compounds were detected at elevated concentrations. Each had a unique chemograph with differences in transport processes (e.g. dependence on flow, dilution processes and timing of concentration pulses). Resampling from the data set was used to assess uncertainty. Bias existed at lower sampling efforts but depended on estimator properties as sampling effort increased: the interpolation, ratio and regression estimators became unbiased. Large differences were observed in precision and the importance of sampling effort and estimator selection depended on the relationship between the chemograph and hydrograph. The variety of transport processes observed and the resultant variability in uncertainty suggest that useful load estimates can only be obtained with sufficient samples and appropriate estimator selection. We provide a rationale to show the latter can be guided across sampling periods by selecting an estimator where the sampling regime or the relationship between the chemograph and hydrograph meet its assumptions: interpolation becomes more correct as sampling effort increases and the ratio becomes more correct as the r2 correlation between flux and flow increases (e.g. > 0.9); a stratified composite sampling approach, even with random samples, is a promising alternative.