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Rhiannon C. ReVello

Publications and source records attributed to Rhiannon C. ReVello.

7 recordsLinked to original sources
USGS2019

Use of set blanks in reporting pesticide results at the U.S. Geological Survey National Water Quality Laboratory, 2001-15

Executive Summary Background .—Pesticide results from the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) are used for water-quality assessments by many agencies and organizations. The USGS is committed to providing data of the highest possible quality to the consumers of its data. A cooperator’s inquiries about specific pesticide detections in water revealed potential laboratory contamination issues for some results. Consequently, the USGS conducted an extensive evaluation of potential low-level contamination related to processing or analysis of water-quality samples at NWQL for 21 pesticide compounds of interest to the cooperator. This is the most comprehensive study of NWQL pesticide quality-control (QC) results to date. Purpose and scope .—The purpose of this study was to document protocols used by the NWQL to censor pesticide results and to determine the effects of laboratory contamination—as determined from detections in laboratory set blanks—on pesticide detections in groundwater and surface-water samples. More than 30,000 pesticide results from 113 selected batches of samples (2 percent or less of total batches) analyzed by the NWQL during the 15 years from 2001 to 2015 were reviewed. All laboratory results from the selected batches, including results from environmental (surface water and groundwater) and QC (set-blank, blind-blank, and blind-spike) samples, were evaluated. The study includes results for 21 pesticide compounds analyzed in groundwater and surface-water samples collected across the United States. Eleven pesticide compounds were analyzed by a gas chromatography/mass spectrometry method and 10 compounds by a liquid chromatography/mass spectrometry method. Objectives and methods .—The objectives of this study were to (1) determine the characteristics of laboratory contamination over time, (2) compare distributions of pesticide results in set blanks with distributions in environmental samples, (3) evaluate the potential for false-positive and false-negative reporting of results, and (4) evaluate the effects of reevaluating historical pesticide results using 2017 compound identification protocols on detections of pesticides in groundwater and surface-water samples. The 113 instrument batches selected for this study contained detections of one or more of the 21 pesticide compounds in set blanks or were among those batches with the highest pesticide detection frequencies in set blanks. As a result, the dataset for this study was targeted toward pesticides and batches with laboratory contamination. The objectives were addressed by statistically comparing environmental and set-blank results; computing moving averages of set-blank detection frequencies to identify periods of episodic contamination; and using summary statistics, tabular summaries, and graphical approaches, such as time-series plots and cumulative distribution functions. Results .— Objective 1 : Laboratory contamination, as determined by pesticide detections in set blanks, was found in 13 percent of set-blank results from the 113 targeted batches included in this study (as compared to 6 percent of set-blank results from all 7,620 batches analyzed during the study period). It is estimated that 92 percent of the laboratory contamination during the study period was episodic, meaning that it occurred during discrete periods of time. All 21 of the targeted pesticide compounds had periods of episodic contamination, with most episodes ranging in duration from about 1 to 8 months. The remaining 8 percent of laboratory contamination was random or from a known source (deterministic). Objective 2 : For some compounds, graphs of cumulative distribution functions of the entire distributions of set-blank and environmental samples overlap, suggesting that there is no difference in the distributions of the two types of samples. However, time-series graphs show that detections in set blanks often occur at different times (sometimes separated by years) than detections in environmental samples, indicating clear differences in those distributions, and indicating the importance of evaluating the timing of detections in all sample types. For most compounds detected in set-blank and environmental samples, detection frequencies were significantly greater in set blanks than in groundwater or surface-water samples ( p <0.05). There are several explanations for this finding, including that the 113 batches of samples chosen for this study targeted batches with detections in set blanks or that detections in set-blank samples were historically determined with less stringent identification criteria than for environmental samples (groundwater and surface-water samples). Objective 3 : The false-positive and false-negative rates from blind samples submitted during the study period by the USGS Quality Systems Branch generally were less than 1 and 5 percent, respectively, for the 21 pesticides. The only compound with a false-positive rate greater than 1 percent was flumetsulam (2.6 percent), indicating that there is a higher likelihood of flumetsulam being reported as a detection when it is not present in an environmental sample compared with the reporting of other compounds. Objective 4 : Altogether, for data in targeted batches, NWQL would have reported 0.1 percent of results from groundwater samples and 1.4 percent of results from surface-water samples differently if 2017 identification protocols were applied to historical pesticide results. In most of these cases, detections observed in historical results would change to nondetections. The small percentages of changes that would occur if historical data were reevaluated indicate that historical protocols used by the NWQL to identify detections in environmental samples were robust and produced results that are predominantly consistent with current [2017] practices. Conclusions .—The NWQL produces high-quality pesticide results at environmentally relevant concentrations. NWQL identification protocols and censoring practices are largely effective at minimizing the reporting of false-positive and false-negative results. Laboratory contamination, when it occurred, tended to occur in episodes; thus, evaluating the timing and magnitude of detections in set blanks relative to detections in environmental samples was determined to be an important consideration for analysis of environmental results. Because NWQL censoring practices do not address all types and occurrences of laboratory contamination, options for additional censoring practices are provided for data users with more specific or stringent data-quality objectives. The methods used to analyze the 21 compounds for this report can similarly be applied to all 173 pesticide compounds that were analyzed by the NWQL during the same time period. This study also has helped to identify potential improvements in reporting USGS data, such as conducting more frequent review of set-blank datasets.

Scientific Investigations Report↗
USGS2016

Regional variability in bed-sediment concentrations of wastewater compounds, hormones and PAHs for portions of coastal New York and New Jersey impacted by hurricane Sandy

Bed sediment samples from 79 coastal New York and New Jersey, USA sites were analyzed for 75 compounds including wastewater associated contaminants, PAHs, and other organic compounds to assess the post-Hurricane Sandy distribution of organic contaminants among six regions. These results provide the first assessment of wastewater compounds, hormones, and PAHs in bed sediment for this region. Concentrations of most wastewater contaminants and PAHs were highest in the most developed region (Upper Harbor/Newark Bay, UHNB) and reflected the wastewater inputs to this area. Although the lack of pre-Hurricane Sandy data for most of these compounds make it impossible to assess the effect of the storm on wastewater contaminant concentrations, PAH concentrations in the UHNB region reflect pre-Hurricane Sandy conditions in this region. Lower hormone concentrations than predicted by the total organic carbon relation occurred in UHNB samples, suggesting that hormones are being degraded in the UHNB region.

New Jersey, New York↗
USGS2013

An isotope-dilution standard GC/MS/MS method for steroid hormones in water

An isotope-dilution quantification method was developed for 20 natural and synthetic steroid hormones and additional compounds in filtered and unfiltered water. Deuterium- or carbon-13-labeled isotope-dilution standards (IDSs) are added to the water sample, which is passed through an octadecylsilyl solid-phase extraction (SPE) disk. Following extract cleanup using Florisil SPE, method compounds are converted to trimethylsilyl derivatives and analyzed by gas chromatography with tandem mass spectrometry. Validation matrices included reagent water, wastewater-affected surface water, and primary (no biological treatment) and secondary wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100%; with overall relative standard deviation of 28%. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples analyzed in 2009–2010 ranged from 84–104%, with relative standard deviations of 6–36%. Detection levels estimated using ASTM International’s D6091–07 procedure range from 0.4 to 4 ng/L for 17 analytes. Higher censoring levels of 100 ng/L for bisphenol A and 200 ng/L for cholesterol and 3-beta-coprostanol are used to prevent bias and false positives associated with the presence of these analytes in blanks. Absolute method recoveries of the IDSs provide sample-specific performance information and guide data reporting. Careful selection of labeled compounds for use as IDSs is important because both inexact IDS-analyte matches and deuterium label loss affect an IDS’s ability to emulate analyte performance. Six IDS compounds initially tested and applied in this method exhibited deuterium loss and are not used in the final method.

Book chapter↗
USGS2013

Effects of surface applications of biosolids on groundwater quality and trace-element concentrations in crops near Deer Trail, Colorado, 2004-2010

The U.S. Geological Survey (USGS), in cooperation with Metro Wastewater Reclamation District (Metro District), studied biosolids composition and the effects of biosolids applications on groundwater quality and trace-element concentrations in crops of the Metro District properties near Deer Trail, Colorado, during 2004 through 2010. Priority parameters for each monitoring component included the nine trace elements regulated by Colorado for biosolids (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc); other constituents also were analyzed. All concentrations for the priority parameters in monthly biosolids samples were less than Colorado regulatory limits, and the concentrations were relatively consistent. Biosolids likely were the largest source of nitrogen and phosphorus on the Metro District properties. Plutonium isotopes were not detected in the biosolids, but many organic wastewater compounds (organic wastewater compounds: wastewater indicators, pharmaceuticals, and hormones) were detected in substantial concentrations relative to minimum reporting levels and various surface-water concentrations. Bismuth, copper, mercury, nitrogen, phosphorus, silver, biogenic sterols, detergent degradates, disinfectants, fire retardants, fragrances, pharmaceuticals, and plasticizers would be the most likely biosolids signature to indicate the presence of Metro District biosolids in soil or streambed sediment from the study area. Antimony, cadmium, cobalt, copper, molybdenum, nickel, nitrogen, phosphorus, selenium, tungsten, vanadium, zinc, detergent degradates, disinfectants, fire retardants, fragrances, pharmaceuticals or their degradates, and plasticizers would be the most likely biosolids signature for groundwater and surface water in the study area. More biosolids-signature components detected and larger concentration differences from untreated materials, baseline, and blank samples indicate more evidence of biosolids presence or effects. Although the inorganic constituent concentrations were relatively large in samples from one monitoring well, the concentrations of organic wastewater compounds in groundwater samples were not correspondingly large. Concentrations of organic wastewater compounds in the groundwater samples from all five monitoring wells were less than the minimum reporting levels with only a few detections. Some of the organic wastewater compounds detected could have anthropogenic sources that are not biosolids. Concentrations of priority parameters in groundwater varied spatially and temporally but generally were less than Colorado regulatory limits. Concentrations of dissolved nitrate, arsenic, and selenium, in addition to chloride, sulfate, total dissolved solids, boron, iron, manganese, and uranium, in samples from some wells exceeded the Colorado standards. Concentrations of dissolved nitrate (three wells), molybdenum (one well), selenium (two wells), and uranium (one well) in shallow groundwater had significant (alpha = 0.05) upward trends in some parts of the study area. The biosolids-signature results indicate that the aquifers intercepted by the five routinely sampled wells likely have received some recharge through treated (biosolids-applied) fields or biosolids-affected ponds. Adverse effects from this biosolids-related recharge range from few (if any) at one well to large and significantly (alpha = 0.05) increasing nitrate concentrations at another well. A statistical evaluation of five paired wheat-grain samples from treated (biosolids-applied) fields and untreated (control) fields did not indicate any evidence that biosolids applications significantly (alpha = 0.05 or 0.10) increased concentration of any of these constituents in wheat grain. The wheat-grain concentrations from this study were similar to those from other studies for fields in North America where no biosolids were applied. The data for the limited crop samples indicate that biosolids applications are not increasing the concentrations of arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, sulfur, and zinc in mature wheat grain from the study area.

Colorado↗
USGS2012

Determination of steroid hormones and related compounds in filtered and unfiltered water by solid-phase extraction, derivatization, and gas chromatography with tandem mass spectrometry

A new analytical method has been developed and implemented at the U.S. Geological Survey National Water Quality Laboratory that determines a suite of 20 steroid hormones and related compounds in filtered water (using laboratory schedule 2434) and in unfiltered water (using laboratory schedule 4434). This report documents the procedures and initial performance data for the method and provides guidance on application of the method and considerations of data quality in relation to data interpretation. The analytical method determines 6 natural and 3 synthetic estrogen compounds, 6 natural androgens, 1 natural and 1 synthetic progestin compound, and 2 sterols: cholesterol and 3--coprostanol. These two sterols have limited biological activity but typically are abundant in wastewater effluents and serve as useful tracers. Bisphenol A, an industrial chemical used primarily to produce polycarbonate plastic and epoxy resins and that has been shown to have estrogenic activity, also is determined by the method. A technique referred to as isotope-dilution quantification is used to improve quantitative accuracy by accounting for sample-specific procedural losses in the determined analyte concentration. Briefly, deuterium- or carbon-13-labeled isotope-dilution standards (IDSs), all of which are direct or chemically similar isotopic analogs of the method analytes, are added to all environmental and quality-control and quality-assurance samples before extraction. Method analytes and IDS compounds are isolated from filtered or unfiltered water by solid-phase extraction onto an octadecylsilyl disk, overlain with a graded glass-fiber filter to facilitate extraction of unfiltered sample matrices. The disks are eluted with methanol, and the extract is evaporated to dryness, reconstituted in solvent, passed through a Florisil solid-phase extraction column to remove polar organic interferences, and again evaporated to dryness in a reaction vial. The method compounds are reacted with activated -methyl--trimethylsilyl trifluoroacetamide at 65 degrees Celsius for 1 hour to form trimethylsilyl or trimethylsilyl-enol ether derivatives that are more amenable to gas chromatographic separation than the underivatized compounds. Analysis is carried out by gas chromatography with tandem mass spectrometry using calibration standards that are derivatized concurrently with the sample extracts. Analyte concentrations are quantified relative to specific IDS compounds in the sample, which directly compensate for procedural losses (incomplete recovery) in the determined and reported analyte concentrations. Thus, reported analyte concentrations (or analyte recoveries for spiked samples) are corrected based on recovery of the corresponding IDS compound during the quantification process. Recovery for each IDS compound is reported for each sample and represents an absolute recovery in a manner comparable to surrogate recoveries for other organic methods used by the National Water Quality Laboratory. Thus, IDS recoveries provide a useful tool for evaluating sample-specific analytical performance from an absolute mass recovery standpoint. IDS absolute recovery will differ and typically be lower than the corresponding analyte’s method recovery in spiked samples. However, additional correction of reported analyte concentrations is unnecessary and inappropriate because the analyte concentration (or recovery) already is compensated for by the isotope-dilution quantification procedure. Method analytes were spiked at 10 and 100 nanograms per liter (ng/L) for most analytes (10 times greater spike levels were used for bisphenol A and 100 times greater spike levels were used for 3--coprostanol and cholesterol) into the following validation-sample matrices: reagent water, wastewater-affected surface water, a secondary-treated wastewater effluent, and a primary (no biological treatment) wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100 percent, with overall relative standard deviation of 28 percent. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples and analyzed in 2009–2010 ranged from 84–104 percent, with relative standard deviations of 6–36 percent. Concentrations for two analytes, equilin and progesterone, are reported as estimated because these analytes had excessive bias or variability, or both. Additional database coding is applied to other reported analyte data as needed, based on sample-specific IDS recovery performance. Detection levels were derived statistically by fortifying reagent water at six different levels (0.1 to 4 ng/L) and range from about 0.4 to 4 ng/L for 16 analytes. Interim reporting levels applied to analytes in this report range from 0.8 to 8 ng/L. Bisphenol A and the sterols (cholesterol and 3-beta-coprostanol) were consistently detected in laboratory and field blanks. The minimum reporting levels were set at 100 ng/L for bisphenol A and at 200 ng/L for the two sterols to prevent any bias associated with the presence of these compounds in the blanks. A minimum reporting level of 2 ng/L was set for 11-ketotestosterone to minimize false positive risk from an interfering siloxane compound emanating as chromatographic-column bleed, from vial septum material, or from other sources at no more than 1 ng/L.

Techniques and Methods↗
USGS2011

Endocrine active chemicals, pharmaceuticals, and other chemicals of concern in surface water, wastewater-treatment plant effluent, and bed sediment, and biological characteristics in selected streams, Minnesota: Design, methods, and data, 2009

This report presents the study design, environmental data, and quality-assurance data for an integrated chemical and biological study of selected streams or lakes that receive wastewater-treatment plant effluent in Minnesota. This study was a cooperative effort of the U.S. Geological Survey, the Minnesota Pollution Control Agency, St. Cloud State University, the University of St. Thomas, and the University of Colorado. The objective of the study was to identify distribution patterns of endocrine active chemicals, pharmaceuticals, and other organic and inorganic chemicals of concern indicative of wastewater effluent, and to identify biological characteristics of estrogenicity and fish responses in the same streams. The U.S. Geological Survey collected and analyzed water, bed-sediment, and quality-assurance samples, and measured or recorded streamflow once at each sampling location from September through November 2009. Sampling locations included surface water and wastewater-treatment plant effluent. Twenty-five wastewater-treatment plants were selected to include continuous flow and periodic release facilities with differing processing steps (activated sludge or trickling filters) and plant design flows ranging from 0.002 to 10.9 cubic meters per second (0.04 to 251 million gallons per day) throughout Minnesota in varying land-use settings. Water samples were collected from the treated effluent of the 25 wastewater-treatment plants and at one point upstream from and one point downstream from wastewater-treatment plant effluent discharges. Bed-sediment samples also were collected at each of the stream or lake locations. Water samples were analyzed for major ions, nutrients, trace elements, pharmaceuticals, phytoestrogens and pharmaceuticals, alkylphenols and other neutral organic chemicals, carboxylic acids, and steroidal hormones. A subset (25 samples) of the bed-sediment samples were analyzed for carbon, wastewater-indicator chemicals, and steroidal hormones; the remaining samples were archived. Biological characteristics were determined by using an in-vitro bioassay to determine total estrogenicity in water samples and a caged fish study to determine characteristics of fish from experiments that exposed fish to wastewater effluent in 2009. St. Cloud State University deployed and processed caged fathead minnows at 13 stream sites during September 2009 for the caged fish study. Measured fish data included length, weight, body condition factor, and vitellogenin concentrations.

Minnesota↗