Brian Schumacher

Role of Laboratory Sampling Devices and Laboratory Subsampling Methods in Representative Sampling Strategies

Sampling is the act of selecting items from a specified population in order to estimate the parameters of that population (e.g., selecting soil samples to characterize the properties at an environmental site). Sampling occurs at various levels and times throughout an environmental site characterization process. Typically, initial (primary) sampling occurs in the field while subsequent stages of sample size reduction (subsampling) occur until the final laboratory analysis stage. At each step in the measurement process, from planning, site selection, sample collection, sample preparation, through sample analysis, errors can occur that propagate, leading to uncertainty associated with the final result upon which decisions will ultimately be made. The goal of all sampling efforts should be to select samples that are representative of the population (i.e., site) in question. General guidelines, with supporting background and theory, for obtaining representative subsamples for the laboratory analysis of particulate materials using “correct” sampling practices and “correct” sampling devices are presented (“correct” as defined by Gy sampling theory; see Pitard, 1993). Considerations are given to: the constitution and the degree of heterogeneity of the material being sampled, the methods used for sample collection (including what proper tools to use), what it is that the sample is supposed to represent, the mass of the sample needed to be representative, and the bounds of what “representative” actually means.

Evidence of a sewer vapor transport pathway at the USEPA vapor intrusion research duplex

The role of sewer lines as preferential pathways for vapor intrusion is poorly understood. Although the importance of sewer lines for volatile organic compound (VOC) transport has been documented at a small number of sites with vapor intrusion, sewer lines are not routinely sampled during most vapor intrusion investigations. We have used a tracer study and VOC concentration measurements to evaluate the role of the combined sanitary/storm sewer line in VOC transport at the USEPA vapor intrusion research duplex in Indianapolis, Indiana. The results from the tracer study demonstrated gas migration from the sewer main line into the duplex. The migration pathway appears to be complex and may include leakage from the sewer lateral at a location below the building foundation. Vapor samples collected from the sewer line demonstrated the presence of tetrachloroethene (PCE) and chloroform in the sewer main in front of the duplex and at multiple sample locations within the sewer line upstream of the duplex. These test results combined with results from the prior multi-year study of the duplex indicate that the sewer line plays an important role in transport of VOCs from the subsurface source to the immediate vicinity of the duplex building envelope.

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 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.

Comparison of Soil VOCs measured by soil gas, heated headspace, and methanol extraction techniques

Comparisons of soil volatile organic compound (VOC) measurement techniques and soil properties expected to influence these measurements were performed at two dissimilar sites. A total of 41 soil gas, 52 heated headspace, and 51 methanol extraction/purge‐and‐trap measurements were obtained on collocated samples. Contaminants present at both sites included cis‐1,2‐dichloroethene, 1, 1, 1‐trichloroethane, trichloroethene, and tetrachloroethene. Heated headspace offered the highest sensitivity, as indicated by the greatest percentage of detections per number of analyses. The statistical regression between headspace concentrations and methanol extraction concentrations was highly significant (p < 0.001) with r2 = 0.53. Headspace concentrations (range, 7 to 4250 ng/g) ran approximately 20 to 30% of the methanol extraction concentrations (range, 260 to 7300 ng/g), indicating that the methanol was able to extract significantly more of the chlorinated hydrocarbons (CHCs) than the headspace extraction, even in soil...

Ecological risk based assessment used to restore riparian physical functions to a fresh water Creek

The purpose of this study was to determine if an interdisciplinary team using a qualitative proper functioning condition (PFC) assessment protocol could identify and reverse significant detrimental ecological alterations which occurred within Gerties Creek watershed, Ontario, Canada. At potential, Gerties Creek supported a woody debris glacial outwash fine gravel substrate fish spawning habitat. The anthropogenic activities on Georgina Island caused a denuded anadromous fish population since the early-to mid-1990s in the Gerties Creek watershed. The PFC assessment indicated that anthropogenic activities on Georgina Island negatively impacted stream flows in Gerties Creek. Reduced stream flow resulted in the natural stream (lotic) riparian habitat not advancing out of an early seral silver maple and eastern hemlock vegetated swamp (forested wetland) habitat. The Gerties Creek interdisciplinary team PFC assessment indicated that the entire watershed is not in balance with the water and sediment being supplied along with a lack of diverse riparian vegetation. Sediment was not being transported to the wetland and lake coastal areas because of chronic reduced flows. Further qualitative assessments by the authors of other smaller lentic and lotic ecosystems on Georgina Island indicate that reduced hydrologic flow is an issue for the entire island. Ecosystem function management planning works with the ecosystem to continually respond as the ecology changes in ways that enhance remarkable natural recovery.

NOVEL CONTAMINANTS IDENTIFIED IN FISH KILLS IN THE RED RIVER WATERSHED, 2011–2013

Provisional molecular weights and chemical formulas were assigned to 4 significant previously unidentified contaminants present during active fish kills in the Red River region of Oklahoma. The provisional identifications of these contaminants were determined using high-resolution liquid chromatography-time-of-flight mass spectrometry (LC-TOFMS), LC-Fourier transform ion cyclotron resonance mass spectrometry (LC-FTICRMS), and LC-ion trap mass spectrometry (LC-ITMS). Environmental water samples were extracted using a solid-phase extraction (SPE) method, and sediment samples were extracted using a modified sonication liquid extraction method. During screening of the samples, 2 major unknown chromatographic peaks were detected at m/z 624.3 and m/z 639.3. The peak at m/z 639.3 was firmly identified, through the use of an authentic standard, as a porphyrin, specifically chlorin-e6-trimethyl ester, with m/z 639.31735 (M + H)+ and molecular formula C37 H43 N4 O6 . The other major peak, at m/z 624.3 (M + H)+ , was identified as an amide-containing porphyrin. It was discovered that the amide compound was an artifact created during the SPE process by reaction of ammonium hydroxide at 1 of 3 potential reaction sites on chlorin-e6-trimethyl ester. Other unique nontargeted chemicals were also detected and the importance of their identification is discussed. Environ Toxicol Chem 2018;37:336-344. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Temporary vs. Permanent Sub-slab Ports: A Comparative Performance Study

ABSTRACT Vapor intrusion (VI) is the migration of subsurface vapors, including radon and volatile organic compounds (VOCs), from the subsurface to indoor air. The VI exposure pathway extends from the contaminant source, which can be impacted soil or groundwater, to indoor air-exposure points. VOC contaminants of concern typically include halogenated solvents as well as petroleum hydrocarbons. Radon, a colorless radioactive gas that is released by radioactive decay of radionuclides in rock and soil, migrates into homes through VI in a similar fashion to VOCs. This project focused on the performance of permanent versus temporary sub-slab sampling ports for the determination of VI of halogenated VOCs and radon into an unoccupied house. VOC and radon concentrations measured simultaneously in soil gas using collocated temporary and permanent ports appeared to be independent of the type of port. The variability between collocated temporary and permanent ports was much less than the spatial variability between different locations within a single residential duplex. Post sampling leak test results suggested that the temporary SSP desiccation and cracking of the clay portion of the seal were not as detrimental to the port seal performance as would have been expected, this suggests that the Teflon tape portion of the seals served an important function. Pre and post sampling leak tests are advisable when temporary ports are used to collect a time-integrated sample. These results suggest that temporary sub-slab sampling ports can provide data equivalent to that collected from a permanent sub-slab sampling port.

The Effect of Equilibration Time and Tubing Material on Soil Gas Measurements

ABSTRACT The collection of soil vapor samples representative of in-situ conditions presents challenges associated with the unavoidable disturbance of the subsurface and potential losses to the atmosphere. This article evaluates the effects of two variables that influence the concentration of volatile organic compounds in soil vapor samples: equilibration time and tubing material. The time for three types of soil vapor probes (i.e., macro-purge, mini-purge, and post-run tubing probes [PRT]) to equilibrate with subsurface conditions was assessed by installing probes and collecting multiple samples over a 72-hour period. The effect of tubing material was evaluated by collocating soil vapor probes constructed with different tubing material and collecting samples over several months. We recommend that soil vapor probes constructed with a sand filter-pack and bentonite seal (i.e., macro-purge probe) equilibrate for 24 to 48 hours prior to sample collection. Post-run tubing (PRT) probes equilibrated within one to two hours while a new probe design, (i.e., mini-purge probe) equilibrated and could be sampled after only 30 minutes for screening assessments. Nylaflow, Teflon®, polyetheretherketone (PEEK), and stainless-steel tubing had comparable trichloroethene (TCE) concentrations over all sampling time frames. We recommend that copper tubing be avoided and polyethylene only be used for screening assessments.