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Advances in spectroscopic methods for quantifying soil carbon

The current gold standard for soil carbon (C) determination is elemental C analysis using dry combustion. However, this method requires expensive consumables, is limited by the number of samples that can be processed (~100/d), and is restricted to the determination of total carbon. With increased interest in soil C sequestration, faster methods of analysis are needed, and there is growing interest in methods based on diffuse reflectance spectroscopy in the visible, near-infrared or mid-infrared spectral ranges. These spectral methods can decrease analytical requirements and speed sample processing, be applied to large landscape areas using remote sensing imagery, and be used to predict multiple analytes simultaneously. However, the methods require localized calibrations to establish the relationship between spectral data and reference analytical data, and also have additional, specific problems. For example, remote sensing is capable of scanning entire watersheds for soil carbon content but is limited to the surface layer of tilled soils and may require difficult and extensive field sampling to obtain proper localized calibration reference values. The objective of this chapter is to discuss the present state of spectroscopic methods for determination of soil carbon.

Book chapter

Pharmaceuticals in water, fish and osprey nestlings in Delaware River and Bay

Exposure of wildlife to Active Pharmaceutical Ingredients (APIs) is likely to occur but studies of risk are limited. One exposure pathway that has received attention is trophic transfer of APIs in a water-fish-osprey food chain. Samples of water, fish plasma and osprey plasma were collected from Delaware River and Bay, and analyzed for 21 APIs. Only 2 of 21 analytes exceeded method detection limits in osprey plasma (acetaminophen and diclofenac) with plasma levels typically 2–3 orders of magnitude below human therapeutic concentrations (HTC). We built upon a screening level model used to predict osprey exposure to APIs in Chesapeake Bay and evaluated whether exposure levels could have been predicted in Delaware Bay had we just measured concentrations in water or fish. Use of surface water and BCFs did not predict API concentrations in fish well, likely due to fish movement patterns, and partitioning and bioaccumulation uncertainties associated with these ionizable chemicals. Input of highest measured API concentration in fish plasma combined with pharmacokinetic data accurately predicted that diclofenac and acetaminophen would be the APIs most likely detected in osprey plasma. For the majority of APIs modeled, levels were not predicted to exceed 1 ng/mL or method detection limits in osprey plasma. Based on the target analytes examined, there is little evidence that APIs represent a significant risk to ospreys nesting in Delaware Bay. If an API is present in fish orders of magnitude below HTC, sampling of fish-eating birds is unlikely to be necessary. However, several human pharmaceuticals accumulated in fish plasma within a recommended safety factor for HTC. It is now important to expand the scope of diet-based API exposure modeling to include alternative exposure pathways (e.g., uptake from landfills, dumps and wastewater treatment plants) and geographic locations (developing countries) where API contamination of the environment may represent greater risk.

Delaware, New Jersey, Pennsylvania

Weathering of oil in a surficial aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C 6‐30 n ‐alkanes, toluene, and o ‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐ C 10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ 13 C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.

Minnesota

An appeal to undergraduate wildlife programs: send scientists to learn statistics

Undergraduate wildlife students taking introductory statistics too often are poorly prepared and insufficiently motivated to learn statistics. We have also encountered too many wildlife professionals, even with graduate degrees, who exhibit an aversion to thinking statistically, either relying too heavily on statisticians or avoiding statistics altogether. We believe part of the reason for these problems is that wildlife majors are insufficiently grounded in the scientific method and analytical thinking before they take statistics. We suggest that a partial solution is to assure wildlife majors are trained in the scientific method at the very beginning of their academic careers.

Wildlife Society Bulletin

PHT3D-UZF: A reactive transport model for variably-saturated porous media

A modified version of the MODFLOW/MT3DMS-based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably-saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D-UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated-zone flow (UZF1) package. A volume-averaged approach similar to the method used in UZF-MT3DMS was adopted. The PHREEQC-based computation of chemical processes within PHT3D-UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional-scale applications, UZF1 simulates downward-only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably-saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.

Ground Water

A source-depth separation filter: Using the Euler method on the derivatives of total intensity magnetic anomaly data

Derivatives of potential-field anomalies (or the anomaly gradients) enhance the field associated with shallow features and de-emphasize the field from deeper sources. The derivative approach of separating anomalies of shallow, intermediate, and deep sourves is, however, qualitative. Semiautomatic source location methods, such as the Euler method (also variously referred to in the literature as Euler's theorem on homogeneous functions, Euler's differential equation, EULDPH, and Euler deconvolution), the analytic signal method, and Werner deconvolution, developed since the 1980s use anomaly gradients to characterize sources of anomalies (i.e., the type of sources and their locations). In this article, we investigate the benefits of applying the Euler method on derivatives of anomalies to enhance the location of shallow and deep sources. Used appropriately, the method is suitable for characterizing sources from all potential-field data and/or their derivatives, as long as the data can be regarded mathematically as “continuous.” We also explain the reasons why the use of the Euler method on derivatives of anomalies is particularly helpful in the analysis and interpretation of shallow features.

Leading Edge (Tulsa, OK)

Comparison of detection limits estimated using single- and multi-concentration spike-based and blank-based procedures

Spike- and blank-based procedures were applied to estimate the detection limits (DLs) for example analytes from inorganic and organic methods for water samples to compare with the U.S. Environmental Protection Agency's (EPA) Method Detection Limit (MDL) procedures (revisions 1.11 and 2.0). The multi-concentration spike-based procedures ASTM Within-laboratory Critical Level (DQCALC) and EPA's Lowest Concentration Minimum Reporting Level were compared in one application, with DQCALC further applied to many methods. The blank-based DLs, MDL b99 (99th percentile) or MDL bY (= mean blank concentration + s × t ), estimated using large numbers (>100) of blank samples often provide DLs that better approach or achieve the desired ≤1% false positive risk level compared to spike-based DLs. For primarily organic methods that do not provide many uncensored blank results, spike-based DQCALC or MDL rev. 2.0 are needed to simulate the blank distribution and estimate the DL. DQCALC is especially useful for estimating DLs for multi-analyte methods having very different analyte response characteristics. Time series plots of DLs estimated using different procedures reveal that DLs are dependent on the applied procedure, should not be expected to be static over time, and seem best viewed as falling over a range versus being a single value. Use of both blank- and spike-based DL procedures help inform this DL range. Data reporting conventions that censor data at a threshold and report “less than” that threshold concentration as the reporting level have unknown and potentially high false negative risk. The U.S. Geological Survey National Water Quality Laboratory's Laboratory Reporting Level (LRL) convention (applied primarily to organic methods) attempts to simultaneously minimize both the false positive and false negative risk when <LRL is reported and data between DL and the higher LRL are allowed to be reported.

Talanta

In vitro effects-based method and water quality screening model for use in pre- and post-distribution treated waters

Recent urban public water supply contamination events emphasize the importance of screening treated drinking water quality after distribution. In vitro bioassays, when run concurrently with analytical chemistry methods, are effective tools to evaluating the efficacy of water treatment processes and water quality. We tested 49 water samples representing the Chicago Department of Water Management service areas for estrogen, (anti)androgen, glucocorticoid receptor-activating contaminants and cytotoxicity. We present a tiered screening approach suitable to samples with anticipated low-level activity and initially tested all extracts for statistically identifiable endocrine activity; performing a secondary dilution-response analysis to determine sample EC 50 and biological equivalency values (BioEq). Estrogenic activity was detected in untreated Lake Michigan intake water samples using mammalian (5/49; median: 0.21 ng E2Eq/L) and yeast cell (5/49; 1.78 ng E2Eq/L) bioassays. A highly sensitive (anti)androgenic activity bioassay was applied for the first time to water quality screening and androgenic activity was detected in untreated intake and treated pre-distribution samples (4/49; 0.93 ng DHTEq/L). No activity was identified above method detection limits in the yeast androgenic, mammalian anti-androgenic, and both glucocorticoid bioassays. Known estrogen receptor agonists were detected using HPLC/MS-MS (estrone: 0.72-1.4 ng/L; 17α-estradiol: 1.3-1.5 ng/L; 17β-estradiol: 1.4 ng/L; equol: 8.8 ng/L), however occurrence did not correlate with estrogenic bioassay results. Many studies have applied bioassays to water quality monitoring using only relatively small samples sets often collected from surface and/or wastewater effluent. However, to realistically adapt these tools to treated water quality monitoring, water quality managers must have the capacity to screen potentially hundreds of samples in short timeframes. Therefore, we provided a tiered screening model that increased sample screening speed, without sacrificing statistical stringency, and detected estrogenic and androgenic activity only in pre-distribution Chicago area samples.

Illinois, Indiana

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

Calculating depths to shallow magnetic sources using aeromagnetic data from the Tucson Basin

Using gridded high-resolution aeromagnetic data, the performance of several automated 3-D depth-to-source methods was evaluated over shallow control sources based on how close their depth estimates came to the actual depths to the tops of the sources. For all three control sources, only the simple analytic signal method, the local wavenumber method applied to the vertical integral of the magnetic field, and the horizontal gradient method applied to the pseudo-gravity field provided median depth estimates that were close (-11% to +14% error) to the actual depths. Careful attention to data processing was required in order to calculate a sufficient number of depth estimates and to reduce the occurrence of false depth estimates. For example, to eliminate sampling bias, high-frequency noise and interference from deeper sources, it was necessary to filter the data before calculating derivative grids and subsequent depth estimates. To obtain smooth spatial derivative grids using finite differences, the data had to be gridded at intervals less than one percent of the anomaly wavelength. Before finding peak values in the derived signal grids, it was necessary to remove calculation noise by applying a low-pass filter in the grid-line directions and to re-grid at an interval that enabled the search window to encompass only the peaks of interest. Using the methods that worked best over the control sources, depth estimates over geologic sites of interest suggested the possible occurrence of volcanics nearly 170 meters beneath a city landfill. Also, a throw of around 2 kilometers was determined for a detachment fault that has a displacement of roughly 6 kilometers.

Arizona

Mapping the distribution of materials in hyperspectral data using the USGS Material Identification and Characterization Algorithm (MICA)

Identifying materials by measuring and analyzing their reflectance spectra has been an important method in analytical chemistry for decades. Airborne and space-based imaging spectrometers allow scientists to detect materials and map their distributions across the landscape. With new satellite-borne hyperspectral sensors planned for the future, for example, HYSPIRI (HYPerspectral InfraRed Imager), robust methods are needed to fully exploit the information content of hyperspectral remote sensing data. A method of identifying and mapping materials using spectral feature based analysis of reflectance data in an expert-system framework called MICA (Material Identification and Characterization Algorithm) is described in this paper. The core concepts and calculations of MICA are presented. A MICA command file has been developed and applied to map minerals in the full-country coverage of the 2007 Afghanistan HyMap hyperspectral data.

Conference Paper

Modified QuEChERS extraction for the analysis of young-of-year smallmouth bass using GC × GC-TOFMS

Signs of disease, such as external lesions, have been prevalent in smallmouth bass throughout the Susquehanna River Basin, USA. Previous targeted chemical studies in this system have identified known persistent organic pollutants, but a common explanatory link across multiple affected sites remains undetermined. A fast and robust extraction method that can be applied to young-of-year fish is needed to effectively screen for target and non-target compounds that may be impacting organism health. The quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction methodology was optimized to perform both targeted and non-targeted chemical analyses from a single extraction of whole young-of-year fish. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS) was used for extract analysis. Sample extraction was performed using the solvent ethyl acetate, followed by a two-step cleanup in which samples were frozen for lipid removal and subjected to dispersive solid phase extraction using Florisil. A sample of 21 young-of-year smallmouth bass collected from areas with disease and exhibiting different types of external lesions were evaluated for 233 target compounds. A total of 34 organic contaminants, including polychlorinated biphenyls, brominated diphenyl ethers, organochlorinated pesticides, and personal care products, were detected. Data from this sample set was then analyzed for non-targets. Using the Fisher ratio method and multivariate analysis, an additional 10 significant features were identified specific to either fish with visible lesions or with no visible disease characteristics.

Pennsylvania

De facto water reuse: Bioassay suite approach delivers depth and breadth in endocrine active compound detection

Although endocrine disrupting compounds (EDCs) have been detected in wastewater and surface waters worldwide using a variety of in vitro effects-based screening tools, e.g. bioassays, few have examined potential attenuation of environmental contaminants by both natural (sorption, degradation, etc) and anthropogenic (water treatment practices) processes. This study used several bioassays and quantitative chemical analyses to assess residence-time weighted samples at six sites along a river in the northeastern United States beginning upstream of a waste water treatment plant (WWTP) outfall and proceeding downstream along the stream reach to a drinking water treatment plant (DWTP). Known steroidal estrogens were quantified and changes in signaling pathway molecular initiating events (activation of estrogen, androgen, glucocorticoid, peroxisome proliferator-activated, pregnane X receptor, and aryl hydrocarbon receptor signaling networks) were identified in water extracts. In initial multi-endpoint assays geographic and receptor-specific endocrine activity patterns in transcription factor signatures and nuclear receptor activation were discovered. In subsequent single endpoint receptor-specific bioassays, estrogen (16 of 18 samples; 0.01 to 28 ng estradiol equivalents [E2Eqs]/L) glucocorticoid (3 of 18 samples; 1.8 to 21 ng dexamethasone equivalents [DexEqs]/L), and androgen (2 of 18 samples; 0.95 to 2.1 ng dihydrotestosterone equivalents [DHTEqs]/L) receptor transcriptional activation occurred above respective assay method detection limits (0.04 ng E2Eqs/L, 1.2 ng DexEqs/L, and 0.77 ng DHTEqs/L) in multiple sampling events. Estrogen activity, the most often detected, correlated well with measured concentrations of known steroidal estrogens (R2 = 0.890). Overall, activity indicative of multiple types of endocrine active compounds was highest in wastewater effluent samples, while activity downstream was progressively lower, and negligible in (unfinished) treated water. This multiple bioassay approach, in conjunction with targeted analytical chemistry methods, has gained acceptance among water quality screening programs. Not only was estrogenic and glucocorticoid activity confirmed in the effluent by utilizing multiple methods concurrently, but other activated signaling networks that historically received less attention (i.e. peroxisome proliferator-activated receptor) were also detected.

Science of the Total Environment

Improved vertical streambed flux estimation using multiple diurnal temperature methods in series

Analytical solutions that use diurnal temperature signals to estimate vertical fluxes between groundwater and surface water based on either amplitude ratios ( A r ) or phase shifts (Δ ϕ ) produce results that rarely agree. Analytical solutions that simultaneously utilize A r and Δ ϕ within a single solution have more recently been derived, decreasing uncertainty in flux estimates in some applications. Benefits of combined ( A r Δ ϕ ) methods also include that thermal diffusivity and sensor spacing can be calculated. However, poor identification of either A r or Δ ϕ from raw temperature signals can lead to erratic parameter estimates from A r Δ ϕ methods. An add-on program for VFLUX 2 is presented to address this issue. Using thermal diffusivity selected from an A r Δ ϕ method during a reliable time period, fluxes are recalculated using an A r method. This approach maximizes the benefits of the A r and A r Δ ϕ methods. Additionally, sensor spacing calculations can be used to identify periods with unreliable flux estimates, or to assess streambed scour. Using synthetic and field examples, the use of these solutions in series was particularly useful for gaining conditions where fluxes exceeded 1 m/d.

Groundwater

Actively heated high-resolution fiber-optic-distributed temperature sensing to quantify streambed flow dynamics in zones of strong groundwater upwelling

Zones of strong groundwater upwelling to streams enhance thermal stability and moderate thermal extremes, which is particularly important to aquatic ecosystems in a warming climate. Passive thermal tracer methods used to quantify vertical upwelling rates rely on downward conduction of surface temperature signals. However, moderate to high groundwater flux rates (>−1.5 m d −1 ) restrict downward propagation of diurnal temperature signals, and therefore the applicability of several passive thermal methods. Active streambed heating from within high-resolution fiber-optic temperature sensors (A-HRTS) has the potential to define multidimensional fluid-flux patterns below the extinction depth of surface thermal signals, allowing better quantification and separation of local and regional groundwater discharge. To demonstrate this concept, nine A-HRTS were emplaced vertically into the streambed in a grid with ∼0.40 m lateral spacing at a stream with strong upward vertical flux in Mashpee, Massachusetts, USA. Long-term (8–9 h) heating events were performed to confirm the dominance of vertical flow to the 0.6 m depth, well below the extinction of ambient diurnal signals. To quantify vertical flux, short-term heating events (28 min) were performed at each A-HRTS, and heat-pulse decay over vertical profiles was numerically modeled in radial two dimension (2-D) using SUTRA. Modeled flux values are similar to those obtained with seepage meters, Darcy methods, and analytical modeling of shallow diurnal signals. We also observed repeatable differential heating patterns along the length of vertically oriented sensors that may indicate sediment layering and hyporheic exchange superimposed on regional groundwater discharge.

Water Resources Research

Comparison of two estrogen chemically activated luciferase expression cell bioassays to liquid chromatography–mass spectrometry for quantifying estrone in water samples

Chemically activated luciferase expression (CALUX) cell bioassays are popular tools for assessing endocrine activity of chemicals such as certain environmental contaminants. Although activity equivalents can be obtained from CALUX analysis, directly comparing these equivalents to those obtained from analytical chemistry methods can be problematic because of the complexity of endocrine active pathways. We explored the suitability of two estrogen CALUX bioassays (the Organisation for Economic Co-operation and Development–approved VM7Luc4E2 cell bioassay and the VM7LucERβc9 cell bioassay) for quantitation of estrogen. Quadrupole-time of flight ultraperformance liquid chromatography–mass spectrometry (LC/MS) was selected as a comparative method. Regression analysis of measured estrone (E1) calibration samples showed all three methods to be highly predictive of nominal concentrations ( p ≤ 7.5 × 10 –51 ). Extracts of water sampled from laboratory dilutor tanks containing E1 at 0, 20, and 200 ng/L alone and in combination with atrazine were selected to test the quantitative capabilities of the CALUX assays. Process controls (0 and 100 ng E1/L) and a separate E1 standard (10 ng/ml, used to prepare the E1 process control) were also tested. Levels of E1 determined by LC/MS analysis and bioanalytical equivalents (ng E1/L) determined by CALUX analyses were comparable except in certain instances where the samples required dilution prior to CALUX analyses (e.g., the E1 process control and E1 standard). In those instances, measurements by CALUX were slightly but significantly decreased relative to LC/MS. Atrazine had no effect on the ability of either LC/MS or the CALUX bioassays to quantify E1. The present study illustrates the CALUX bioassays as successful in quantifying an estrogen in simple water samples and further characterizes their utility for screening. Environ Toxicol Chem 2023;42:333–339. Published 2022. This article is a U.S. Government work and is in the public domain in the USA.

Environmental Toxicology and Chemistry

Considerations and challenges in support of science and communication of fish consumption advisories for per- and polyfluoroalkyl substances

Federal, state, tribal, or local entities in the United States issue fish consumption advisories (FCAs) as guidance for safer consumption of locally caught fish containing contaminants. Fish consumption advisories have been developed for commonly detected compounds such as mercury and polychlorinated biphenyls. The existing national guidance does not specifically address the unique challenges associated with bioaccumulation and consumption risk related to per- and polyfluoroalkyl substances (PFAS). As a result, several states have derived their own PFAS-related consumption guidelines, many of which focus on one frequently detected PFAS, known as perfluorooctane sulfonic acid (PFOS). However, there can be significant variation between tissue concentrations or trigger concentrations (TCs) of PFOS that support the individual state-issued FCAs. This variation in TCs can create challenges for risk assessors and risk communicators in their efforts to protect public health. The objective of this article is to review existing challenges, knowledge gaps, and needs related to issuing PFAS-related FCAs and to provide key considerations for the development of protective fish consumption guidance. The current state of the science and variability in FCA derivation, considerations for sampling and analytical methodologies, risk management, risk communication, and policy challenges are discussed. How to best address PFAS mixtures in the development of FCAs, in risk assessment, and establishment of effect thresholds remains a major challenge, as well as a source of uncertainty and scrutiny. This includes developments better elucidating toxicity factors, exposures to PFAS mixtures, community fish consumption behaviors, and evolving technology and analytical instrumentation, methods, and the associated detection limits. Given the evolving science and public interests informing PFAS-related FCAs, continued review and revision of FCA approaches and best practices are vital. Nonetheless, consistent, widely applicable, PFAS-specific approaches informing methods, critical concentration thresholds, and priority compounds may assist practitioners in PFAS-related FCA development and possibly reduce variability between states and jurisdictions. Integr Environ Assess Manag 2024;00:1–20. © 2024 SETAC

Integrated Environmental Assessment and Management

Response to "Comment on and Reinterpretation of Gabriel et al. (2014) "Fish Mercury and Surface Water Sulfate Relationships in the Everglades Protection Area""

The purpose of this forum is to respond to a rebuttal submitted by Julian et al., Environ Manag 55:1–5, 2015 where they outlined their overall disagreement with the data preparation, methods, and interpretation of results presented in Gabriel et al. (Environ Manag 53:583–593, 2014 ). Here, we provide background information on the research premise presented in Gabriel et al. (Environ Manag 53:583–593, 2014 ) and provide a defense for this work using five themes. In spite of what Julian et al. perceive as limitations in the sampling methods and analytical tools used for this work, the relationships found between fish total mercury and surface water sulfate concentrations in Gabriel et al. (Environ Manag 53:583–593, 2014 ) are comparable to relationships between pore water methylmercury (MeHg) and pore water sulfate found in past studies indicating that sulfate is important to MeHg production and bioaccumulation in the Everglades. Julian et al. state “…there is no way to justify any ecosystem-wide sulfur strategy as a management approach to reduce mercury risk in the (Everglades) as suggested by Gabriel et al. (Environ Manag 53:583–593, 2014 ), Corrales et al. (Sci Tot Environ 409:2156–2162, 2011 ) and Orem et al. (Rev Environ Sci Technol 41 (S1):249–288, 2011 ).” We disagree, and having stated why sulfate input reduction to the Everglades may be the most effective means of reducing mercury in Everglades fish, it is important that research on sulfur and mercury biogeochemistry continues. If further studies support the relationship between sulfate loading reduction and MeHg reduction, sulfur mass balance studies should commence to (1) better quantify agricultural and connate seawater sulfate inputs and (2) define opportunities to reduce sulfate inputs to the Everglades ecosystem.

Environmental Management