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Mark R. Burkhardt

Publications and source records attributed to Mark R. Burkhardt.

14 recordsLinked to original sources
USGS2014

Determination of human-use pharmaceuticals in filtered water by direct aqueous injection: high-performance liquid chromatography/tandem mass spectrometry

This report describes a method for the determination of 110 human-use pharmaceuticals using a 100-microliter aliquot of a filtered water sample directly injected into a high-performance liquid chromatograph coupled to a triple-quadrupole tandem mass spectrometer using an electrospray ionization source operated in the positive ion mode. The pharmaceuticals were separated by using a reversed-phase gradient of formic acid/ammonium formate-modified water and methanol. Multiple reaction monitoring of two fragmentations of the protonated molecular ion of each pharmaceutical to two unique product ions was used to identify each pharmaceutical qualitatively. The primary multiple reaction monitoring precursor-product ion transition was quantified for each pharmaceutical relative to the primary multiple reaction monitoring precursor-product transition of one of 19 isotope-dilution standard pharmaceuticals or the pesticide atrazine, using an exact stable isotope analogue where possible. Each isotope-dilution standard was selected, when possible, for its chemical similarity to the unlabeled pharmaceutical of interest, and added to the sample after filtration but prior to analysis. Method performance for each pharmaceutical was determined for reagent water, groundwater, treated drinking water, surface water, treated wastewater effluent, and wastewater influent sample matrixes that this method will likely be applied to. Each matrix was evaluated in order of increasing complexity to demonstrate (1) the sensitivity of the method in different water matrixes and (2) the effect of sample matrix, particularly matrix enhancement or suppression of the precursor ion signal, on the quantitative determination of pharmaceutical concentrations. Recovery of water samples spiked (fortified) with the suite of pharmaceuticals determined by this method typically was greater than 90 percent in reagent water, groundwater, drinking water, and surface water. Correction for ambient environmental concentrations of pharmaceuticals hampered the determination of absolute recoveries and method sensitivity of some compounds in some water types, particularly for wastewater effluent and influent samples. The method detection limit of each pharmaceutical was determined from analysis of pharmaceuticals fortified at multiple concentrations in reagent water. The calibration range for each compound typically spanned three orders of magnitude of concentration. Absolute sensitivity for some compounds, using isotope-dilution quantitation, ranged from 0.45 to 94.1 nanograms per liter, primarily as a result of the inherent ionization efficiency of each pharmaceutical in the electrospray ionization process. Holding-time studies indicate that acceptable recoveries of pharmaceuticals can be obtained from filtered water samples held at 4 °C for as long as 9 days after sample collection. Freezing samples to provide for storage for longer periods currently (2014) is under evaluation by the National Water Quality Laboratory.

Techniques and Methods↗
USGS2013

Dissipation of contaminants of emerging concern in biosolids applied to non-irrigated farmland in eastern Colorado

In 2007, a 1.5-year field-scale study was initiated by the U.S. Geological Survey to evaluate the dissipation of contaminants of emerging concern (CECs) following a first agronomic biosolids application to nonirrigated farmland. CECs with the greatest decrease in concentration in the surface biosolids at 180 days post-application included indole, d-limonene, p-cresol, phenol, and skatol. CECs that were present in the largest concentration in 180-day-weathered biosolids included stanols, nonylphenols, bisphenol A, bis(2-ethylhexyl) phthalate, hexahydrohexamethyl cyclopenta-benzopyran (HHCB), and triclosan. CECs that were detected in pre-application soil were 3-beta coprostanol, skatol, acetophenone, beta-sitosterol, beta-stigmastanol, cholesterol, indole, p-cresol, and phenol, most of which are biogenic sterols or fragrances that have natural plant sources in addition to anthropogenic sources, yet their concentrations increased (in some cases, substantially) following biosolids application. Preliminary data indicate the nonylphenols (including NPEO1, NPEO2), OPEO1, benzo[a]pyrene, diethyl phthalate, d-limonene, HHCB, triclosan, and possibly 3-beta coprostanol, skatol, beta-sitosterol, cholesterol, indole, and p-cresol, migrated downward through the soil by 468 days post-application, but indicated little uptake by mature wheat plants. This study indicates that some CECs are sufficiently persistent and mobile to be vertically transported into the soil column following biosolids applications to the land surface, even in semiarid regions.

Journal of the American Water Resources Associatio↗
USGS2012

Earthworm bioassays and seedling emergence for monitoring toxicity, aging and bioaccumulation of anthropogenic waste indicator compounds in biosolids-amended soil

Land application of biosolids (treated sewage sludge) can be an important route for introducing xenobiotic compounds into terrestrial environments. There is a paucity of available information on the effects of biosolids amendment on terrestrial organisms. In this study, the influence of biosolids and biosolids aging on earthworm (Eisenia fetida) reproduction and survival and lettuce (Lactuca sativa) seedling emergence was investigated. Earthworms were exposed to soils amended with varying quantities of biosolids (0, 1, 2, 3, or 4% dry mass). To investigate the influence of biosolids aging, the biosolids used in the study were aged for differing lengths of time (2 or 8 weeks) prior to exposure. All of the adult earthworms survived in the biosolids–amended soils at all concentrations that were aged for 2 weeks; however, only 20% of the adults survived in the soil amended with the highest concentration of biosolids and aged for 8 weeks. Reproduction as measured by mean number of juveniles and unhatched cocoons produced per treatment correlated inversely with biosolids concentration, although the effects were generally more pronounced in the 8-week aged biosolids–soil samples. Latent seedling emergence and reduced seedling fitness correlated inversely with biosolids concentration, but these effects were tempered in the 8-week aged versus the 2-week aged soil–biosolids mixtures. Anthropogenic waste indicator compounds (AWIs) were measured in the biosolids, biosolids–soil mixtures, and earthworm samples. Where possible, bioaccumulation factors (BAFs) were calculated or estimated. A wide variety of AWIs were detected in the biosolids (51 AWIs) and earthworm samples (≤ 19 AWI). The earthworms exposed to the 8-week aged biosolids–soil mixtures tended to accumulate greater quantities of AWIs compared to the 2-week aged mixture, suggesting that the bioavailability of some AWIs was enhanced with aging. The BAFs for a given AWI varied with treatment. Notably large BAFs were determined for some AWIs. For example, the maximum BAF determined for para-cresol, methyl salicylate, bisphenol-A, and cholesterol was greater than 100 in some treatments.

Science of the Total Environment↗
USGS2007

Effects of Hurricanes Katrina and Rita on the chemistry of bottom sediments in Lake Pontchartrain, La.

Concerns about the effect of pumping contaminated flood waters into Lake Pontchartrain following the hurricanes of 2005 prompted the U.S. Geological Survey (USGS) to sample street mud, canal-suspended sediment, and bottom sediment in Lake Pontchartain. The samples were analyzed for a wide variety of potential inorganic and organic contaminants. Results indicate that contamination of lake sediment relative to other urban lakes and to accepted sedimentquality guidelines was limited to a relatively small area offshore from the Metairie Outfall Canal (popularly known as the 17th Street Canal) and that this contamination is probably transient.

Louisiana↗
USGS2006

Chapter 3. Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry

A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and passed through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry. Comparisons of PAH data for 28 sediment samples extracted by Soxhlet and the accelerated solvent extraction (ASE) method described in this report produced similar results. Extraction of PAH compounds from standard reference material using this method also compared favorably with Soxhlet extraction. The recoveries of PAHs less than molecular weight 202 (pyrene or fluoranthene) are higher by up to 20 percent using this ASE method, whereas the recoveries of PAHs greater than or equal to molecular weight 202 are equivalent. This ASE method of sample extraction of solids has advantages over conventional Soxhlet extraction by increasing automation of the extraction process, reducing extraction time, and using less solvent. Extract cleanup also is greatly simplified because SPE replaces commonly used gel permeation chromatography. The performance of the method (as expressed by mean recoveries and mean precision) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. Recoveries of PAH and semivolatile compounds in Ottawa sand samples fortified at 1.5 micrograms averaged 88 percent ? 9.4 percent relative standard deviation, and calculated initial method detection limits per compound averaged 14 micrograms per kilogram, assuming a 25-gram sample size. The recovery for 1,2,4-trichlorobenzene is less than 60 percent; thus, the concentration of this compound will always be reported as estimated with the E remark code. The analysis of 25 alkylated PAH homolog groups also can be determined with this method with extra data analysis and review, but because of the lack of authentic reference standard compounds, these results are considered to be semiquantitative. The PAH homolog groups are quantitated using the response factor of a parent PAH method compound, if available. Precision data for the alkylated PAH homologs detected in a marine sediment standard reference material (SRM 1944) also are presented to document and demonstrate method capability.

Techniques and Methods↗
USGS2002

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Arsenic speciation in natural-water samples using laboratory and field methods

Analytical methods for the determination of arsenite [As(III)], arsenate [As(V)], dimethylarsinate (DMA), monomethylarsonate (MMA), and roxarsone in filtered natural-water samples are described. Various analytical methods can be used for the determination, depending on the arsenic species being determined. Arsenic concentration is determined by using inductively coupled plasma-mass spectrometry (ICP-MS) as an arsenic-specific detector for all methods. Laboratory-speciation methods are described that use an ion chromatographic column to separate the arsenic species; the column length, column packing, and mobile phase are dependent on the species of interest. Regardless of the separation technique, the arsenic species are introduced into plasma by eithe rpneumatic nebulization or arsine generation. Analysis times range from 2 to 8 minutes and method detection limits range from 0.1 to 0.6 microgram-arsenic per liter (ug-As/L), 10 to 60 picograms absolute (for a 100-microliter injection), depending on the arsenic species determined and the analytical method used. A field-generation specciation method also is described that uses a strong anion exchange cartridge to separate As(III) from As(V) in the field. As(III) in the eluate and the As(V) in the cartridge extract are determined by direct nebulization ICP-MS. Methylated arsenic species that also are retained on the cartridge will positively bias As(V) results without further laboratory separations. The method detection limit for field speciation is 0.3 ug-As/L. The distribution of arsenic species must be preserved in the field to eliminate changes caused by photochemical oxidation or metal oxyhydroxide precipitation. Preservation techniques, such as refrigeration, the addition of acides, or the additoin of ethylene-diaminetetraacetic acid (EDTA) and the effects of ambient light were tested. Of the preservatives evaluated, EDTA was found to work best with the laboratory- and field-speciation methods for all sample matrices tested. Storing the samples in opaque polytethylene bottles eliminated the effects of photochemical oxidation. The percentage change in As(III):As(V) ratios for an EDTA-preserved acid mine drainage (AMD) sample and ground-water sample during a 3-month period was -5 percent and +3 percent, respectively. The bias and variability of the methods were evaluated by comparing results for total arsenic and As(III), As(V), DMA, and MMA concentrations in ground water, AMD, and surface water. Seventy-one ground-water, 10 AMD, and 24 surface-water samples were analyzed. Concentrations in ground-water samples reached 720 ug-As/L for As(III) and 1080 ug-As/L for As(V); AMD samples reached 12800 ug-As/L for As(III) and 7050 ug-As/L for As(V); and surface-water samples reached 5 ug-As/L for As(III) and As(V). Inorganic arsenic species distribution in the samples ranged from 0 to 90 percent As(III). DMA and MMA were present only in surface-water samples from agricultural areas where the herbicide monosodium methylarsonate was applied; concentrations never exceeded 6 ug-As/L. Statistical analyses indicated that the difference between As(III) and As(V) concentrations for samples preserved with EDTA in opaque bottles and field-speciation results were analytically insignificant at the 95-percent confidence interval. There was no significant difference among the methods tested for total arsenic concentration. Percentage recovery for field samples spiked at 50 ug-As/L and analyzed by the laboratory-speciation method (n=2) ranged from 82 to 100 percent for As(III), 97 to 102 percent for As(V), 90 to 104 percent for DMA, and 81 to 96 percent for MMA; recoveries for samples spiked at 100 ug-As/L and analyzed by the field-speciation method ranged from 102 to 107 percent for As(III) and 105 to 106 percent for As(V). Laboratory-speciation results for Environment Canada reference material SLRS-2 closely matched reported concentrations. Laboratory-speciation metho

Water-Resources Investigations Report↗
USGS2002

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of wastewater compounds by polystyrene-divinylbenzene solid-phase extraction and capillary-column gas chromatography/mass spectrometry

A method for the determination of 67 compounds typically found in domestic and industrial wastewater is described. The method was developed in response to increasing concern over the impact of endocrine-disrupting chemicals in wastewater on aquatic organisms. This method also may be useful for evaluating the impact of combined sanitary and storm-sewer overflow on the water quality of urban streams. The method focuses on the determination of compounds that are an indicator of wastewater or that have been chosen on the basis of their endocrine-disrupting potential or toxicity. These compounds include the alkylphenol ethoxylate nonionic surfactants and their degradates, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclicaromatic hydrocarbons, and high-use domestic pesticides. Water samples are filtered to remove suspended particulate matter and then are extracted by vacuum through disposable solid-phase cartridges that contain polystyrene-divinylbenzene resin. Cartridges are dried with nitrogen gas, and then sorbed compounds are eluted with dichloromethane-diethyl ether (4:1) and determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-water samples fortified at 4 micrograms per liter averaged 74 percent ? 7 percent relative standard deviation for all method compounds. Initial method detection limits for single-component compounds (excluding hormones and sterols) averaged 0.15 microgram per liter. Samples are preserved by filtration, the addition of 60 grams NaCl, and storage at 4 degrees Celsius. The laboratory has established a sample-holding time (prior to sample extraction) of 14 days from the date of sample collection until a statistically accepted method can be used to determine the effectiveness of these sample-preservation procedures.

Water-Resources Investigations Report↗
USGS2001

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of pesticides in water by graphitized carbon-based solid-phase extraction and high-performance liquid chromatography/mass spectrometry

In 1996, the U.S. Geological Survey National Water Quality Laboratory (NWQL) developed and implemented a graphitized carbon-based solid-phase extraction and high-performance liquid chromatographic analytical method to determine polar pesticide concentrations in surface- and ground-water samples. Subsequently, the NWQL developed a complementary analysis that uses high-performance liquid chromatography/mass spectrometry to detect, identify, and quantify polar pesticides and pesticide metabolites in filtered water at concentrations as low as 10 nanograms per liter. This new method was designed to improve sensitivity and selectivity over the prior method, and to reduce known interferences from natural organic matter. In this new method, pesticides are extracted from filtered water samples by useing a 0.5-gram graphitized carbon-based solid-phase extraction cartridge, eluted from the cartridge, and concentrations determined by using high-performance liquid chromatography with electrospray ionization-mass spectrometry. The upper concentration limit is 1.000 microgram per liter ( μ g /L) for most compounds. Single-operator method detection limits in organic-free water samples fortified with pesticides at a concentration of 0.025 μg/L ranged from 0.0019 to 0.022 μ g /L for all compounds in the method. The grand mean (mean of mean recoveries for individual compounds) recoveries in organic-free water samples ranged from 72 to 89 percent, fortified with pesticides at three concentrations between 0.025 and 0.5 μ g /L. Grand mean recoveries in ground- and surface-water samples ranged from 46 to 119 percent, also fortified with pesticides at three concentrations between 0.025 and 0.5 μ g /L. Long-term recoveries from reagent water spikes were used to demonstrate that 38 of 65 compounds can be reported without qualification of the quantitative result across the analytical range of the method. The remaining 27 are reported with qualified estimates of concentration because of greater variability of recovery.

Water-Resources Investigations Report↗
USGS2001

Concentration of selected sulfonylurea, sulfonamide, and imidazolinone herbicides, other pesticides, and nutrients in 71 streams, 5 reservoir outflows, and 25 wells in the Midwestern United States, 1998

Sulfonylurea (SU), sulfonamide (SA), and imidazolinone (IMI) herbicides are recently developed herbicides that function by inhibiting the action of a key plant enzyme, stopping plant growth, and eventually killing the plant. These compounds generally have low mammalian toxicity, but crop and non-crop plants demonstrate a wide range in sensitivity to SUs, SAs, and IMIs, with over a 10,000-fold difference in observed toxicity levels for some compounds. SUs, SAs, and IMIs are applied either pre- or post-emergence to crops commonly at 1/50th or less of the rate of other herbicides. Little is known about their occurrence, fate, or transport in surface water or ground water in the United States. To obtain information on the occurrence of SU, SA, and IMI herbicides in the Midwestern United States, 214 water samples were collected from 76 surface-water and 25 ground-water sites in 1998. These samples were analyzed for 16 SU, SA, and IMI herbicides by using highperformance liquid chromatography/mass spectrometry. Samples also were analyzed for 46 pesticides and pesticide degradation products and 13 herbicides and 10 herbicide degradates. At least 1 of the 16 SUs, SAs, or IMIs was detected at or above the method reporting limit of 0.010 microgram per liter (ug/L) in 83 percent of 133 stream samples. Imazethapyr was detected most frequently (69 percent of samples), followed by flumetsulam (65 percent of samples) and nicosulfuron (53 percent of samples). At least one SU, SA, or IMI herbicide was detected at or above the method reporting limit in 6 of 8 reservoir samples and 5 of 25 ground-water samples. SU, SA, and IMI herbicides occurred less frequently and at a fraction (often 1/50th or less) of the concentrations of other herbicides such as atrazine. Acetochlor, atrazine, cyanazine, and metolachlor were all detected in 95 percent or more of 136 stream samples.

Water-Resources Investigations Report↗
USGS1997

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of nonpurgeable suspended organic carbon by wet-chemical oxidation and infrared spectrometry

Precision and accuracy results are described for the determination of nonpurgeable suspended organic carbon (SOC) by silver-filter filtration, wet-chemical oxidation, and infrared determination of hte resulting carbon dioxide (CO2) used at the U.S. Geological Survey's nationalWater Quality Laboratory. An aliquot of raw water isfiltered through a 0.45-micrometer silver filter. The trapped organic material is oxidized using phosphoric acid and potassium persulfate in a scaled glass ampule,and the rseulting CO2 is measured by an infrared CO2 detector. The amount of CO3 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the sample. The SOC method detection limit for routine analysis is 0.2 milligram per liter. The average percent recovery is 97.1 percent and the average standard deviation is 11 percent.

Open-File Report↗
USGS1995

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of methylene blue active substances by spectrophotometry

A method for the determination of methylene blue active substances in whole-water samples by liquid-liquid extraction and spectrophotometric detection is described. Sulfate and sulfonate-based surfectants are reacted with methylene blue to form a blue-colored complex. The complex is extracted into chloroform, back-washed with an acidified phosphate-based buffer solution, and measured against external standards with a probe spectrophotometer. The method detection limt for routine analysis is 0.02 milligram per liter. The precision is plus/minus 10 percent relative standard deviation. The positive bias from nitrate and chloride and U.S. Geological Survey method O-3111-83 for methylene blue active substances is minized by adding a back-washing step.

Open-File Report↗