Passive sampling for volatile organic compounds in indoor air-controlled laboratory comparison of four sampler types.

Correction for 'Passive sampling for volatile organic compounds in indoor air-controlled laboratory comparison of four sampler types' by Todd McAlary et al., Environ. Sci.: Processes Impacts, 2015, 17, 896-905.

Passive sampling for volatile organic compounds in indoor air-controlled laboratory comparison of four sampler types.

This article describes laboratory testing of four passive diffusive samplers for assessing indoor air concentrations of volatile organic compounds (VOCs), including SKC Ultra II, Radiello®, Waterloo Membrane Sampler (WMS) and Automated Thermal Desorption (ATD) tubes with two different sorbents (Tenax TA and Carbopack B). The testing included 10 VOCs (including chlorinated ethenes, ethanes, and methanes, aromatic and aliphatic hydrocarbons), spanning a range of properties and including some compounds expected to pose challenges (naphthalene, methyl ethyl ketone). Tests were conducted at different temperatures (17 to 30 °C), relative humidities (30 to 90% RH), face velocities (0.014 to 0.41 m s(-1)), concentrations (1 to 100 parts per billion by volume [ppbv]) and sampling durations (1 to 7 days). The results show that all of the passive samplers provided data that met the success criteria (relative percent difference [RPD] ≤ 45% of active sample concentrations and coefficient of variation [COV] ≤ 30%) in the majority of cases, but some compounds were problematic for some samplers. The passive sampler uptake rates depend to varying degrees on the sampler, sorbent, target compounds and environmental conditions, so field calibration is advantageous for the highest levels of data quality.

Quantitative passive soil vapor sampling for VOCs--Part 4: Flow-through cell.

This paper presents a controlled experiment comparing several quantitative passive samplers for monitoring concentrations of volatile organic compound (VOC) vapors in soil gas using a flow-through cell. This application is simpler than conventional active sampling using adsorptive tubes because the flow rate does not need to be precisely measured and controlled, which is advantageous because the permeability of subsurface materials affects the flow rate and the permeability of geologic materials is highly variable. Using passive samplers in a flow-through cell, the flow rate may not need to be known exactly, as long as it is sufficient to purge the cell in a reasonable time and minimize any negative bias attributable to the starvation effect. An experiment was performed in a 500 mL flow-through cell using a two-factor, one-half fraction fractional factorial test design with flow rates of 80, 670 and 930 mL min(-1) and sample durations of 10, 15 and 20 minutes for each of five different passive samplers (passive Automatic Thermal Desorption Tube, Radiello®, SKC Ultra, Waterloo Membrane Sampler™ and 3M™ OVM 3500). A Summa canister was collected coincident with each passive sampler and analyzed by EPA Method TO-15 to provide a baseline for comparison of the passive sampler concentrations. The passive sampler concentrations were within a factor of 2 of the Summa canister concentrations in 32 of 35 cases. Passive samples collected at the low flow rate and short duration showed low concentrations, which is likely attributable to insufficient purging of the cell after sampler placement.

Quantitative passive soil vapor sampling for VOCs--part 2: laboratory experiments.

Controlled laboratory experiments were conducted to demonstrate the use of passive samplers for soil vapor concentration monitoring. Five different passive samplers were studied (Radiello, SKC Ultra, Waterloo Membrane Sampler, ATD tubes and 3M OVM 3500). Ten different volatile organic compounds were used of varying classes (chlorinated ethanes, ethanes, and methanes, aliphatics and aromatics) and physical properties (vapor pressure, solubility and sorption). Samplers were exposed in randomized triplicates to concentrations of 1, 10 and 100 ppmv, with a relative humidity of ∼80%, a temperature of ∼24 °C, and a duration of 30 minutes in a chamber with a face velocity of about 5 cm min(-1). Passive samplers are more commonly used for longer sample durations (e.g., 8 hour workday) and higher face velocities (>600 cm min(-1)), so testing to verify the performance for these conditions was needed. Summa canister samples were collected and analyzed by EPA Method TO-15 to establish a baseline for comparison for all the passive samplers. Low-uptake rate varieties of four of the samplers were also tested at 10 ppmv under two conditions; with 5 cm min(-1) face velocity and stagnant conditions to assess whether low or near-zero face velocities would result in a low bias from the starvation effect. The results indicate that passive samplers can provide concentration measurements with accuracy (mostly within a factor of 2) and precision (RSD < 15%) comparable to conventional Summa canister samples and EPA Method TO-15 analysis. Some compounds are challenging for some passive samplers because of uncertainties in the uptake rates, or challenges with retention or recovery.

Quantitative passive soil vapor sampling for VOCs--part 3: field experiments.

Volatile organic compounds (VOCs) are commonly associated with contaminated land and may pose a risk to human health via subsurface vapor intrusion to indoor air. Soil vapor sampling is commonly used to assess the nature and extent of VOC contamination, but can be complicated because of the wide range of geologic material permeability and moisture content conditions that might be encountered, the wide variety of available sampling and analysis methods, and several potential causes of bias and variability, including leaks of atmospheric air, adsorption-desorption interactions, inconsistent sampling protocols and varying levels of experience among sampling personnel. Passive sampling onto adsorbent materials has been available as an alternative to conventional whole-gas sample collection for decades, but relationships between the mass sorbed with time and the soil vapor concentration have not been quantitatively established and the relative merits of various commercially available passive samplers for soil vapor concentration measurement is unknown. This paper presents the results of field experiments using several different passive samplers under a wide range of conditions. The results show that properly designed and deployed quantitative passive soil vapor samplers can be used to measure soil vapor concentrations with accuracy and precision comparable to conventional active soil vapor sampling (relative concentrations within a factor of 2 and RSD comparable to active sampling) where the uptake rate is low enough to minimize starvation and the exposure duration is not excessive for weakly retained compounds.

Quantitative passive soil vapor sampling for VOCs--part 1: theory.

Volatile organic compounds are the primary chemicals of concern at many contaminated sites and soil vapor sampling and analysis is a valuable tool for assessing the nature and extent of contamination. Soil gas samples are typically collected by applying vacuum to a probe in order to collect a whole-gas sample, or by drawing gas through a tube filled with an adsorbent (active sampling). There are challenges associated with flow and vacuum levels in low permeability materials, and leak prevention and detection during active sample collection can be cumbersome. Passive sampling has been available as an alternative to conventional gas sample collection for decades, but quantitative relationships between the mass of chemicals sorbed, the soil vapor concentrations, and the sampling time have not been established. This paper presents transient and steady-state mathematical models of radial vapor diffusion to a drilled hole and considerations for passive sampler sensitivity and practical sampling durations. The results indicate that uptake rates in the range of 0.1 to 1 mL min(-1) will minimize the starvation effect for most soil moisture conditions and provide adequate sensitivity for human health risk assessment with a practical sampling duration. This new knowledge provides a basis for improved passive soil vapour sampler design.