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D.A. Alvarez

Publications and source records attributed to D.A. Alvarez.

15 recordsLinked to original sources
USGS2014

Reproductive health indicators of fishes from Pennsylvania watersheds: association with chemicals of emerging concern

Fishes were collected at 16 sites within the three major river drainages (Delaware, Susquehanna, and Ohio) of Pennsylvania. Three species were evaluated for biomarkers of estrogenic/antiandrogenic exposure, including plasma vitellogenin and testicular oocytes in male fishes. Smallmouth bass Micropterus dolomieu , white sucker Catostomus commersonii , and redhorse sucker Moxostoma species were collected in the summer, a period of low flow and low reproductive activity. Smallmouth bass were the only species in which testicular oocytes were observed; however, measurable concentrations of plasma vitellogenin were found in male bass and white sucker. The percentage of male bass with testicular oocytes ranged from 10 to 100 %, with the highest prevalence and severity in bass collected in the Susquehanna drainage. The percentage of males with plasma vitellogenin ranged from 0 to 100 % in both bass and sucker. Biological findings were compared with chemical analyses of discrete water samples collected at the time of fish collections. Estrone concentrations correlated with testicular oocytes prevalence and severity and with the percentage of male bass with vitellogenin. No correlations were noted with the percentage of male sucker with vitellogenin and water chemical concentrations. The prevalence and severity of testicular oocytes in bass also correlated with the percent of agricultural land use in the watershed above a site. Two sites within the Susquehanna drainage and one in the Delaware were immediately downstream of wastewater treatment plants to compare results with upstream fish. The percentage of male bass with testicular oocytes was not consistently higher downstream; however, severity did tend to increase downstream.

Pennsylvania↗
USGS2009

Reproductive health of bass in the potomac, USA, drainage: Part 2. Seasonal occurrence of persistent and emerging organic contaminants

The seasonal occurrence of organic contaminants, many of which are potential endocrine disruptors, entering the Potomac River, USA, watershed was investigated using a two-pronged approach during the fall of 2005 and spring of 2006. Passive samplers (semipermeable membrane device and polar organic chemical integrative sampler [POCIS]) were deployed in tandem at sites above and below wastewater treatment plant discharges within the watershed. Analysis of the samplers resulted in detection of 84 of 138 targeted chemicals. The agricultural pesticides atrazine and metolachlor had the greatest seasonal changes in water concentrations, with a 3.1 - to 91 -fold increase in the spring compared with the level in the previous fall. Coinciding with the elevated concentrations of atrazine in the spring were increasing concentrations of the atrazine degradation products desethylatrazine and desisopropylatrazine in the fall following spring and summer application of the parent compound. Other targeted chemicals (organochlorine pesticides, polycyclic aromatic hydrocarbons, and organic wastewater chemicals) did not indicate seasonal changes in occurrence or concentration; however, the overall concentrations and number of chemicals present were greater at the sites downstream of wastewater treatment plant discharges. Several fragrances and flame retardants were identified in these downstream sites, which are characteristic of wastewater effluent and human activities. The bioluminescent yeast estrogen screen in vitro assay of the POCIS extracts indicated the presence of chemicals that were capable of producing an estrogenic response at all sampling sites. ?? 2009 SETA.

Environmental Toxicology and Chemistry↗
USGS2009

Semivolatile organic compounds in residential air along the Arizona - Mexico border

Concerns about indoor air quality and the potential effects on people living in these environments are increasing as more reports about the toxicities and the potential indoor air exposure levels of household-use chemicals and chemicals fromhousingandfurnishingmanufactureinairarebeingassessed. Gas chromatography/mass spectrometry was used to confirm numerous airborne contaminants obtained from the analysis of semipermeable membrane devices deployed inside of 52 homes situated along the border between Arizona and Mexico. We also describe nontarget analytes in the organochlorine pesticide fractions of 12 of these homes; this fraction is also the most likelytocontainthebroadestscopeofbioconcentratablechemicals accumulated from the indoor air. Approximately 400 individual components were identified, ranging from pesticides to a wide array of hydrocarbons, fragrances such as the musk xylenes, flavors relating to spices, aldehydes, alcohols, esters and phthalate esters, and other miscellaneous types of chemicals. The results presented in this study demonstrate unequivocally that the mixture of airborne chemicals present indoors is far more complex than previously demonstrated. ?? 2009 American Chemical Society.

Environmental Science & Technology↗
USGS2009

Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (k ua ) and no SPMD air partitioning coefficient (K sa ) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining k ua and K sa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The k ua s were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07??m 3 ??g -1 ??d -1 . In cases where uptake was approaching equilibrium, K sa s were approximated. K sa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean k ua values (n??=??3) of anthracene and p,p???-DDE at 0.96 and 1.57??m 3 ??g -1 ??d -1 with relative standard deviations of 8.4% and 8.6% respectively.

Atmospheric Environment↗
USGS2008

Chemical and toxicologic assessment of organic contaminants in surface water using passive samplers

Passive sampling methodologies were used to conduct a chemical and toxicologic assessment of organic contaminants in the surface waters of three geographically distinct agricultural watersheds. A selection of current-use agrochemicals and persistent organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides, were targeted using the polar organic chemical integrative sampler (POCIS) and the semipermeable membrane device passive samplers. In addition to the chemical analysis, the Microtox assay for acute toxicity and the yeast estrogen screen (YES) were conducted as potential assessment tools in combination with the passive samplers. During the spring of 2004, the passive samplers were deployed for 29 to 65 d at Leary Weber Ditch, IN; Morgan Creek, MD; and DR2 Drain, WA. Chemical analysis of the sampler extracts identified the agrochemicals predominantly used in those areas, including atrazine, simazine, acetochlor, and metolachlor. Other chemicals identified included deethylatrazine and deisopropylatrazine, trifluralin, fluoranthene, pyrene, cis- and trans-nonachlor, and pentachloroanisole. Screening using Microtox resulted in no acutely toxic samples. POCIS samples screened by the YES assay failed to elicit a positive estrogenic response. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Journal of Environmental Quality↗
USGS2008

Occurrence of organic wastewater compounds in the Tinkers Creek watershed and two other tributaries to the Cuyahoga River, northeast Ohio

The U.S. Geological Survey - in cooperation with the Ohio Water Development Authority; National Park Service; Cities of Aurora, Bedford, Bedford Heights, Solon, and Twinsburg; and Portage and Summit Counties - and in collaboration with the Ohio Environmental Protection Agency, did a study to determine the occurrence and distribution of organic wastewater compounds (OWCs) in the Tinkers Creek watershed in northeastern Ohio. In the context of this report, OWCs refer to a wide range of compounds such as antibiotics, prescription and nonprescription pharmaceuticals, personal-care products, household and industrial compounds (for example, antimicrobials, fragrances, surfactants, fire retardants, and so forth) and a variety of other chemicals. Canisters containing polar organic integrative sampler (POCIS) and semipermeable membrane device (SPMD) media were deployed instream for a 28-day period in Mayand June 2006 at locations upstream and downstream from seven wastewater-treatment-plant (WWTP) outfalls in the Tinkers Creek watershed, at a site on Tinkers Creek downstream from all WWTP discharges, and at one reference site each in two nearby watersheds (Yellow Creek and Furnace Run) that drain to the Cuyahoga River. Streambed-sediment samples also were collected at each site when the canisters were retrieved. POCIS and SPMDs are referred to as 'passive samplers' because they sample compounds that they are exposed to without use of mechanical or moving parts. OWCs detected in POCIS and SPMD extracts are referred to in this report as 'detections in water' because both POCIS and SPMDs provided time-weighted measures of concentration in the stream over the exposure period. Streambed sediments also reflect exposure to OWCs in the stream over a long period of time and provide another OWC exposure pathway for aquatic organisms. Four separate laboratory methods were used to analyze for 32 antibiotic, 20 pharmaceutical, 57 to 66 wastewater, and 33 hydrophobic compounds. POCIS and streambed-sediment extracts were analyzed by both the pharmaceutical and wastewater methods. POCIS extracts also were analyzed by the antibiotic method, and SPMD extracts were analyzed by the hydrophobic-compound method. Analytes associated with a given laboratory method are referred to in aggregate by the method name (for example, antibiotic-method analytes are referred to as 'antibiotic compounds') even though some analytes associated with the method may not be strictly classified as such. In addition, some compounds were included in the analyte list for more than one laboratory method. For a given sample matrix, individual compounds detected by more than one analytical method are included independently in counts for each method. A total of 12 antibiotic, 20 pharmaceutical, 41 wastewater, and 22 hydrophobic compounds were detected in water at one or more sites. Eight pharmaceutical and 37 wastewater compounds were detected in streambed sediments. The numbers of detections at reference sites tended to be in the low range of detection counts observed in the Tinkers Creek watershed for a given analytical method. Also, the total numbers of compounds detected in water and sediment at the reference sites were less than the total numbers of compounds detected at sites in the Tinkers Creek watershed. With the exception of hydrophobic compounds, it was common at most sites to have more compounds detected in samples collected downstream from WWTP outfalls than in corresponding samples collected upstream from the outfalls. This was particularly true for antibiotic, pharmaceutical, and wastewater compounds in water. In contrast, it was common to have more hydrophobic compounds detected in samples collected upstream from WWTP outfalls than downstream. Caffeine, fluoranthene, N,N-diethyl-meta-toluamide (DEET), phenanthrene, and pyrene were detected in water at all sites in the Tinkers Creek watershed, irrespective of whether the site was upstream or downs

Ohio↗
USGS2006

Trends in monitoring pharmaceuticals and personal-care products in the aquatic environment by use of passive sampling devices

The use of passive sampling in monitoring pharmaceuticals and personal-care products (PPCPs) in the aquatic environment is discussed. The utility of passive sampling methods for monitoring the fraction of heavy metals and the biologically available fraction of non-polar organic priority pollutants is recognized and these technologies are being used in surveys of water quality. These devices are used to measure the dissolved fraction and they can yield information that can be used in the development of risk assessments models. These devices can also be used to locate illegal dumping and to monitor specific sources of input of PPCPs into the environment, or to monitor the effectiveness of water treatment processes in the removal of these compounds from wastewater. These devices can provide representative information at low cost which necessitate a combination of laboratory calibration and field studies for emerging pollutants.

Analytical and Bioanalytical Chemistry↗
USGS2005

Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream

Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.

New Jersey↗
USGS2004

Overview and comparison of lipid-containing semipermeable membrane devices and oysters (Crassostrea gigas) for assessing organic chemical exposure

We performed 20-d, flow-through exposures of lipid-containing semipermeable membrane devices (SPMDs) and Pacific oysters ( Crassostrea gigas ) to three concentrations (nominally 10, 100, and 250 ng/L) of a diverse mixture of polycyclic aromatic hydrocarbons (PAHs). Exposure water was seawater free of particulates larger than 0.1 μm. The results of these controlled laboratory studies demonstrated that SPMDs and oysters concentrate the same chemicals but that the relative amounts accumulated are different. For oysters, the 20-d mean (across treatments) concentration factors (CFs) of test compounds with log K ow ≤ 4.8 were much lower (4.0- to 20-fold lower) than those of the same compounds in SPMDs. In contrast, the 20-d CFs of PAHs with log K ow ≥ 5.6 in oysters from the low-level treatment were higher than the corresponding CFs for SPMDs. The CFs of these compounds in oysters from the low-level treatment ranged from approximately 3.0- to 13-fold higher than those in oysters from the high-level treatment. This physiologically mediated difference in oyster CFs appears to be linked to active feeding in the low-level treatment and to apparent toxicity-induced cessation of feeding (i.e., valve closure) in the high-level treatment. Because CFs for these compounds in oysters were not independent of exposure concentrations, it follows that tissue levels were not proportional to exposure concentration. However, both sampling approaches have advantages and disadvantages, and the appropriateness of their use depends on the goals of a given study.

Environmental Toxicology and Chemistry↗
USGS2004

Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log K ow S < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.

Environmental Toxicology and Chemistry↗
USGS2004

Polar organic chemical integrative sampling and liquid chromatography- electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents

The purpose of the research presented in this paper was twofold: (1) to demonstrate the coupling of two state-of-the-art techniques: a time-weighted polar organic chemical integrative sampler (POCIS) and microliquid chromatography–electrospray/ion-trap mass spectrometry and (2) to assess the ability of these methodologies to detect six drugs (azithromycin, fluoxetine, omeprazole, levothyroxine, methamphetamine, methylenedioxymethamphetamine [MDMA]) in a real-world environment, e.g., waste water effluent. In the effluent from three wastewater treatment plants (WWTPs), azithromycin was detected at concentrations ranging from 15 to 66 ng/L, which is equivalent to a total annual release of 1 to 4 kg into receiving waters. Detected and confirmed in the effluent from two WWTPs were two illicit drugs, methamphetamine and MDMA, at 2 and 0.5 ng/L, respectively. Although the ecotoxicologic significance of drugs in environmental matrices, particularly water, has not been closely examined, it can only be surmised that these substances have the potential to adversely affect biota that are continuously exposed to them even at very low levels. The potential for chronic effects on human health is also unknown but of increasing concern because of the multiuse character of water, particularly in densely populated, arid areas.

Archives of Environmental Contamination and Toxico↗
USGS2004

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.

Chemosphere↗
USGS2004

Purification of triolein for use in semipermeable membrane devices (SPMDs)

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6×) partitioned against methanol. Tests of the procedure show that 14 C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 μg of methyl oleate as compared to sometimes more than 500 μg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.

Chemosphere↗
USGS2001

Development of the permeability/performance reference compound approach for in situ calibration of semipermeable membrane devices

Permeability/performance reference compounds (PRCs) are analytically noninterfering organic compounds with moderate to high fugacity from semipermeable membrane devices (SPMDs) that are added to the lipid prior to membrane enclosure. Assuming that isotropic exchange kinetics (IEK) apply and that SPMD-water partition coefficients are known, measurement of PRC dissipation rate constants during SPMD field exposures and laboratory calibration studies permits the calculation of an exposure adjustment factor (EAF). In theory, PRC-derived EAF ratios reflect changes in SPMD sampling rates (relative to laboratory data) due to differences in exposure temperature, membrane biofouling, and flow velocity-turbulence at the membrane surface. Thus, the PRC approach should allow for more accurate estimates of target solute/vapor concentrations in an exposure medium. Under some exposure conditions, the impact of environmental variables on SPMD sampling rates may approach an order of magnitude. The results of this study suggest that most of the effects of temperature, facial velocity-turbulence, and biofouling on the uptake rates of analytes with a wide range of hydrophobicities can be deduced from PRCs with a much narrower range of hydrophobicities. Finally, our findings indicate that the use of PRCs permits prediction of in situ SPMD sampling rates within 2-fold of directly measured values.

Environmental Science & Technology↗