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USGS2009

Exploratory and spatial data analysis (EDA-SDA) for determining regional background levels and anomalies of potentially toxic elements in soils from Catorce-Matehuala, Mexico

The threshold between geochemical background and anomalies can be influenced by the methodology selected for its estimation. Environmental evaluations, particularly those conducted in mineralized areas, must consider this when trying to determinate the natural geochemical status of a study area, quantifying human impacts, or establishing soil restoration values for contaminated sites. Some methods in environmental geochemistry incorporate the premise that anomalies (natural or anthropogenic) and background data are characterized by their own probabilistic distributions. One of these methods uses exploratory data analysis (EDA) on regional geochemical data sets coupled with a geographic information system (GIS) to spatially understand the processes that influence the geochemical landscape in a technique that can be called a spatial data analysis (SDA). This EDA-SDA methodology was used to establish the regional background range from the area of Catorce-Matehuala in north-central Mexico. Probability plots of the data, particularly for those areas affected by human activities, show that the regional geochemical background population is composed of smaller subpopulations associated with factors such as soil type and parent material. This paper demonstrates that the EDA-SDA method offers more certainty in defining thresholds between geochemical background and anomaly than a numeric technique, making it a useful tool for regional geochemical landscape analysis and environmental geochemistry studies.

Applied Geochemistry↗
USGS2004

Roles of uptake, biotransformation, and target site sensitivity in determining the differential toxicity of chlorpyrifos to second to fourth instar Chironomous riparius (Meigen)

Early life stages of aquatic organisms tend to be more sensitive to various chemical contaminants than later life stages. This research attempted to identify the key biological factors that determined sensitivity differences among life stages of the aquatic insect Chironomous riparius. Specifically, second to fourth instar larvae were exposed in vivo to both low and high waterborne concentrations of chlorpyrifos to examine differences in accumulation rates, chlorpyrifos biotransformation, and overall sensitivity among instars. In vitro acetylcholinesterase (AChE) assays were performed with chlorpyrifos and the metabolite, chlorpyrifos-oxon, to investigate potential target site sensitivity differences among instars. Earlier instars accumulated chlorpyrifos more rapidly than later instars. There were no major differences among instars in the biotransformation rates of chlorpyrifos to the more polar metabolites, chlorpyrifos-oxon, and chlorpyridinol (TCP). Homogenate AChE activities from second to fourth instar larvae were refractory to chlorpyrifos, even at high concentrations. In contrast, homogenate AChE activities were responsive in a dose-dependent manner to chlorpyrifos-oxon. In general, it appeared that chlorpyrifos sensitivity differences among second to fourth instar C. riparius were largely determined by differences in uptake rates. In terms of AChE depression, fourth instar homogenates were more sensitive to chlorpyrifos and chlorpyrifos-oxon than earlier instars. However, basal AChE activity in fourth instar larvae was significantly higher than basal AChE activity in second to third instar larvae, which could potentially offset the apparent increased sensitivity to the oxon. ?? 2003 Elsevier B.V. All rights reserved.

Aquatic Toxicology↗
USGS2008

Effects of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in zebrafish: General and reproductive toxicity

Mixed-sex populations of young adult zebrafish (???2-month-old) were exposed to measured RDX concentrations of 0, 1 or 9.6 ppm for up to 12 weeks followed by a 15-day rearing period in untreated water. RDX caused high mortality at 9.6 ppm, with most deaths occurring within the first 8 weeks of exposure. RDX at 9.6 ppm caused lower body weights at 4 and 8 weeks of exposure; and at 1 ppm, lower body weight was observed only at 4 weeks. Fish length was not affected by treatment at any time during the exposure period. The bioconcentration factor for RDX seemed to be influenced by time of exposure but not by water RDX concentration; its overall values were 1.01 ?? 0.13, 0.91 ?? 0.06 and 2.23 ?? 0.04 at 4, 8 weeks and 12 weeks, respectively. RDX was not detected in fish collected after the 15-day recovery period. In a separate experiment, adult females and males were separately exposed to RDX at measured concentrations of 0, 0.5 and 3.2 ppm for a period of 6 weeks. Reproductive performance was evaluated by biweekly breeding of the fish and measuring packed-egg volume (PEV) as index of fecundity. At 0.5 ppm, RDX caused elevated PEV levels relative to the control value at 2 weeks but not at 4 or 6 weeks, whereas no significant effects were noted at 3.2 ppm. Egg fertilization and embryo hatching rates were not affected by RDX at any of the concentrations tested. In conclusion, RDX at sublethal concentrations causes short-term negative effects on growth and, at 0.5 ppm, positive effects on fecundity. ?? 2008 Elsevier Ltd.

Chemosphere↗
USGS2013

Response of diatoms and silicoflagellates to climate change in the Santa Barbara Basin during the past 250 years and the rise of the toxic diatom Pseudo-nitzschia australis

Diatoms and silicoflagellate assemblages were examined in two year-increments of varved samples spanning the interval from 1748 through 2007 in Santa Barbara Basin (SBB) box core SBBC0806 to determine the timing and impact of possible 20th century warming on several different components of the plankton. Diatoms (Thalassionema nitzschioides =TN) and silicoflagellates (Distephanus speculum s.l. =DS) indicative of cooler waters and a shallow thermocline begin to decline in the 1920s and persistently compose a lower percentage of the assemblage in the SBB by about 1940. Prior to 1940, TN constituted on average ~30% of the Chaetoceros-free diatom sediment assemblage and DS on average ~36% of the silicoflagellate assemblage. Between 1940 and 1996 these relative abundances were ~20% (TN) and ~8% (DS). These results are consistent with results from planktonic foraminifera and radiolarians that indicate an influence of 20th century warming on marine ecosystems before most scientific observations began. Cooling of surface waters coincident with the one of the strongest La Niña events of the 20th century (and a return to negative PDO conditions) in late 1998 brought about a return to pre-1940 values of these cool water taxa (TN ~31%, DS ~25%). However, this recent regional cooling appears to have been accompanied by profound changes in the diatom assemblage. Pseudo-nitzschia australis, and Pseudo-nitzschia multiseries, diatom species associated with domoic acid, a neurotoxin that causes shellfish poisoning and marine mammal deaths, rapidly became dominant in the SBB sediment record at the time of the regional cooling (1999) and increased substantially in numbers as a bloom-forming taxon (relative to Chaetoceros spores) in 2003. Prior to 2003 diatom blooms recorded in the SBB sediment record consisted predominantly of Chaetoceros spores and less commonly of Rhizosolenia-related species (Neocalyptrella robusta and R. setigera). Fecal pellets dominated by valves of P. australis, however, were particularly abundant in both the 2003 and 2006 samples, coincident with recorded incidents of domoic acid increase and widespread shellfish poisoning in the SBB.

Quaternary International↗
USGS2009

Developmental toxicity in white leghorn chickens following in ovo exposure to perfluorooctane sulfonate (PFOS)

Studies show that perfluorinated compounds cause various toxicological effects; nevertheless, effects on immune function and developmental endpoints have not been addressed at length. This study examined the effects of perfluorooctane sulfonate (PFOS) in white leghorn hatchlings on various developmental, immunological, and clinical health parameters. In addition, serum PFOS concentrations were determined by LC/MS/MS. Embryonic day (ED) 0 eggs were injected with either safflower oil/10% DMSO (control, 0 mg/kg egg wt) or PFOS in safflower oil/10% DMSO at 1, 2.5, or 5 mg/kg egg wt, and the chicks were grown to post-hatch day (PHD) 14. Treatment with PFOS did not affect hatch rate. Following in ovo exposure chicks exhibited increases in spleen mass at all treatment levels, in liver mass at 2.5 and 5 mg/kg egg wt, and in body length (crown-rump length) at the 5 mg/kg treatment. Right wings were shorter in all treatments compared to control. Increases in the frequency of brain asymmetry were evident in all treatment groups. SRBC-specific immunoglobulin (IgM and IgY combined) titers were decreased significantly at all treatment levels, while plasma lysozyme activity was increased at all treatment levels. The PHA skin test response decreased in relation to increasing PFOS dose. Serum concentrations where significant immunological, morphological, and neurological effects were observed at the lowest dose (1 mg/kg egg wt) averaged 154 ng PFOS/g serum. These concentrations fall within environmental ranges reported in blood samples from wild caught avian species; thereby, verifying that the environmental egg concentrations used for the injections do indeed relate to serum levels in hatchlings that are also environmentally relevant. These data indicate that immune alterations and brain asymmetry can occur in birds following in ovo exposure to environmentally relevant concentrations of PFOS and demonstrates the need for further research on the developmental effects of perfluorinated compounds in various species. ?? 2009 Elsevier Inc.

Reproductive Toxicology↗
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↗
USGS2016

Organic contaminants in Great Lakes tributaries: Prevalence and potential aquatic toxicity

Organic compounds used in agriculture, industry, and households make their way into surface waters through runoff, leaking septic-conveyance systems, regulated and unregulated discharges, and combined sewer overflows, among other sources. Concentrations of these organic waste compounds (OWCs) in some Great Lakes tributaries indicate a high potential for adverse impacts on aquatic organisms. During 2010&ndash;13, 709 water samples were collected at 57 tributaries, together representing approximately 41% of the total inflow to the lakes. Samples were collected during runoff and low-flow conditions and analyzed for 69 OWCs, including herbicides, insecticides, polycyclic aromatic hydrocarbons, plasticizers, antioxidants, detergent metabolites, fire retardants, non-prescription human drugs, flavors/fragrances, and dyes. Urban-related land cover characteristics were the most important explanatory variables of concentrations of many OWCs. Compared to samples from nonurban watersheds (< 15% urban land cover) samples from urban watersheds (> 15% urban land cover) had nearly four times the number of detected compounds and four times the total sample concentration, on average. Concentration differences between runoff and low-flow conditions were not observed, but seasonal differences were observed in atrazine, metolachlor, DEET, and HHCB concentrations. Water quality benchmarks for individual OWCs were exceeded at 20 sites, and at 7 sites benchmarks were exceeded by a factor of 10 or more. The compounds with the most frequent water quality benchmark exceedances were the PAHs benzo[ a ]pyrene, pyrene, fluoranthene, and anthracene, the detergent metabolite 4-nonylphenol, and the herbicide atrazine. Computed estradiol equivalency quotients (EEQs) using only nonsteroidal endocrine-active compounds indicated medium to high risk of estrogenic effects (intersex or vitellogenin induction) at 10 sites. EEQs at 3 sites were comparable to values reported in effluent. This multifaceted study is the largest, most comprehensive assessment of the occurrence and potential effects of OWCs in the Great Lakes Basin to date.

Great Lakes↗
USGS2003

Review of residue-based selenium toxicity thresholds for freshwater fish

A variety of guidelines have been proposed in recent years for linking selenium concentrations in the whole body of fish or in diet with adverse effects in fish. Diverging viewpoints seem to be forming separating groups supporting either the low-selenium guidelines proposed by the government and academic researchers or the high-selenium guidelines proposed by other researchers. Recently, an article was published that reviewed selected studies and recommended guidelines for selenium concentrations in the whole body of fish and in diet that were higher than those proposed by other researchers (≈4 μg/g in whole body and 3–4 μg/g in diet). That article also recommended separating guidelines for coldwater fish (6 μg/g in whole body and 11 μg/g in diet) and warmwater fish (9 μg/g in whole body and 10 μg/g in diet). The approaches, information, and guidelines presented in the article are reviewed and problems in their interpretation and conclusions are discussed. The majority of the selenium literature supports a whole-body threshold of 4 μg/g in fish and 3 μg/g in diet.

Ecotoxicology and Environmental Safety↗
USGS2001

Interparticle migration of metal cations in stream sediments as a factor in toxics transport

Sorption of metal cations by stream sediments is an important process affecting the movement of released contaminants in the environment. The ability of cations to desorb from one sediment particle and subsequently sorb to another can greatly affect metal transport rates but rates for this process have not been reported. The objective of this study was to determine the rate at which sorbed metals can migrate from contaminated sediment particles to uncontaminated sediment particles as a function of the concentration of the contaminating solution and the duration of the contact with the contaminating solution. Samples of small sediment particles were exposed to solutions containing cobalt, after which they were rinsed and combined with larger uncontaminated sediment particles in the presence of stream water. Initial concentrations of the contaminating solution ranged from 1ng/l to 1000mg/l and exposures to the contaminating solution ranged from 6h to 14 days. The rate of the migration increased with increasing concentrations in the contaminating solution and with decreasing times of exposure to the contaminating solution. Under the conditions of these experiments, the time required for the migration to reach equilibrium was on the order of months or longer. In separate experiments, the kinetics of adsorption and desorption of cobalt were measured as a function of concentration of the contaminating solution. The time required to reach adsorption equilibrium increased with increasing concentration in the contaminating solution. Times to sorption equilibrium were on the order of months. Desorption was much slower than adsorption and, together with intraparticle diffusion, probably controls the rate of migration from contaminated to uncontaminated sediment. The results of this study show that interparticle migration of metal cations can proceed at significant rates that are strongly influenced by the length of time that the metal has been in contact with the sediment. Copyright ?? 2001 Elsevier Science B.V.Sorption of metal cations by stream sediments is an important process affecting the movement of released contaminants in the environment. The ability of cations to desorb from one sediment particle and subsequently sorb to another can greatly affect metal transport rates but rates for this process have not been reported. The objective of this study was to determine the rate at which sorbed metals can migrate from contaminated sediment particles to uncontaminated sediment particles as a function of the concentration of the contaminating solution and the duration of the contact with the contaminating solution. Samples of small sediment particles were exposed to solutions containing cobalt, after which they were rinsed and combined with larger uncontaminated sediment particles in the presence of stream water. Initial concentrations of the contaminating solution ranged from 1 ng/l to 1000 mg/l and exposures to the contaminating solution ranged from 6 h to 14 days. The rate of the migration increased with increasing concentrations in the contaminating solution and with decreasing times of exposure to the contaminating solution. Under the conditions of these experiments, the time required for the migration to reach equilibrium was on the order of months or longer. In separate experiments, the kinetics of adsorption and desorption of cobalt were measured as a function of concentration of the contaminating solution. The time required to reach adsorption equilibrium increased with increasing concentration in the contaminating solution. Times to sorption equilibrium were on the order of months. Desorption was much slower than adsorption and, together with intraparticle diffusion, probably controls the rate of migration from contaminated to uncontaminated sediment. The results of this study show that interparticle migration of metal cations can proceed at significant rates that are strongly influenced by the length of time that the metal has

Journal of Hazardous Materials↗
USGS1991

Reproductive outcomes in colonial fish-eating birds: A biomarker for developmental toxicants in Great Lakes food chains: II. Spatial variation in the occurrence and prevalence of bill defects in young double-crested cormorants in the Great Lakes, 1979–1987

Congenital malformations are relatively uncommon in most wild bird populations. Here we document the occurrence of bill malformations in double-crested cormorant ( Phalacrocorax auritus ) chicks from colonies in Green Bay and elsewhere in the Great Lakes and in reference areas off the Great Lakes, in the years 1979 through 1987. In the Great Lakes, 31,168 cormorant chicks were examined during 147 visits to 42 colonies. Seventy of these chicks had crossed or deflected bills or bills in which the mandibles differed in length. Only two of the 20,962 chicks examined during 82 visits to 35 colonies in reference areas located in the prairies and northwestern Ontario had bill defects. The probability of observing a malformed chick on a visit to a colony in Green Bay was 10 to 32 times greater than on a visit to a colony in the reference areas. Bill defects were observed at only two (6%) of the colonies in the reference areas. This proportion was exceeded in six of eight geographic regions within the Great Lakes and was highest (73%) in Green Bay colonies. The prevalence of malformed chicks in Green Bay (52.1 per 10,000)was markedly greater than in all other regions during this period. These bill defects are an example of developmental asymmetry and are an indicator of developmental stability within local populations. Other investigations in Lake Michigan suggest that chemicals such as polyhalogenated aromatic hydrocarbons (e.g., PCBs) that induce aryl hydrocarbon hydroxylase are responsible for the defects observed defects.

Great Lakes↗
USGS2018

Potential toxicity of complex mixtures in surface waters from a nationwide survey of United States streams: Identifying in vitro bioactivities and causative chemicals

While chemical analysis of contaminant mixtures remains an essential component of environmental monitoring, bioactivity-based assessments using in vitro systems increasingly play a role in the detection of biological effects. Historically, in vitro assessments focused on a few biological pathways, e.g., aryl hydrocarbon receptor (AhR) or estrogen receptor (ER) activities. High-throughput screening (HTS) technologies have greatly increased the number of biological targets and processes that can be rapidly assessed. Here we screened extracts of surface waters from nationwide survey of United States (US) streams for bioactivities associated with 69 different endpoints using two multiplexed HTS assays. Bioactivity of extracts from 38streams was evaluated and compared with concentrations of over 700 analytes to identify chemicals contributing to observed effects. Eleven primary biological endpoints were detected. Pregnane X receptor and AhR-mediated activities were the most commonly detected. Measured chemicals did not completely account for AhR and PXR responses. Surface waters with AhR and PXR effects were associated with low intensity, developed land-cover. Likewise, elevated bioactivities frequently associated with wastewater discharges included endocrine related endpoints— ER and glucocorticoid receptor (GR). These results underscore the value of bioassay-based monitoring of environmental mixtures for detecting biological effects that could not be ascertained solely through chemical analyses.

Environmental Science & Technology↗
USGS2019

Phytoplankton community and algal toxicity at a recurring bloom in Sullivan Bay, Kabetogama Lake, Minnesota, USA

Kabetogama Lake in Voyageurs National Park, Minnesota, USA suffers from recurring late summer algal blooms that often contain toxin-producing cyanobacteria. Previous research identified the toxin microcystin in blooms, but we wanted to better understand how the algal and cyanobacterial community changed throughout an open water season and how changes in community structure were related to toxin production. Therefore, we sampled one recurring bloom location throughout the entire open water season. The uniqueness of this study is the absence of urban and agricultural nutrient sources, the remote location, and the collection of samples before any visible blooms were present. Through quantitative polymerase chain reaction (qPCR), we discovered that toxin-forming cyanobacteria were present before visible blooms and toxins not previously detected in this region (anatoxin-a and saxitoxin) were present, indicating that sampling for additional toxins and sampling earlier in the season may be necessary to assess ecosystems and human health risk.

Minnesota↗
USGS2009

Developmental toxicity of diphenyl ether herbicides in nestling American kestrels

Beginning the day after hatching, American kestrel (Falco sparverius) nestlings were orally dosed for 10 consecutive days with 5 microliters/g of corn oil (controls) or one of the diphenyl ether herbicides (nitrofen, bifenox, or oxyfluorfen) at concentrations of 10, 50, 250, or 500 mg/kg in corn oil. At 500 mg/kg, nitrofen resulted in complete nestling mortality, bifenox in high (66%) mortality, and oxyfluorfen in no mortality. Nitrofen at 250 mg/kg reduced nestling growth as reflected by decreased body weight, crownrump length, and bone lengths including humerus, radiusulna, femur, and tibiotarsus. Bifenox at 250 mg/kg had less effect on growth than nitrofen, but crownrump, humerus, radiusulna, and femur were significantly shorter than controls. Liver weight as a percent of body weight increased with 50 and 250 mg/kg nitrofen. Other manifestations of impending hepatotoxicity following nitrofen ingestion included increased hepatic GSH peroxidase activity in all nitrofentreated groups, and increased plasma enzyme activities for ALT, AST, and LDHL in the 250mg/kg group. Bifenox ingestion resulted in increased hepatic GSH peroxidase activity in the 50and 250mg/kg groups. Nitrofen exposure also resulted in an increase in total plasma thyroxine (T4) concentration. These findings suggest that altricial nestlings are more sensitive to diphenyl ether herbicides than young or adult birds of precocial species.

Journal of Toxicology and Environmental Health↗
USGS2003

Assessing toxicant effects in a complex estuary--A case study of effects of silver on reproduction in the bivalve, Potamocurbula amurensis, in San Francisco Bay

Contaminant exposures in natural systems can be highly variable. This variability is superimposed upon cyclic variability in biological processes. Together, these factors can confound determination of contaminant effects. Long term, multidisciplined studies with high frequency sampling can be effective in overcoming such obstacles. While studying trace metal contamination in the tissues of the clam, Potamocorbula amurensis , in the northern reach of San Francisco Bay, an episode of high Ag concentrations was identified (maximum of 5.5 µg g −1 ) at two mid-estuary sites. High concentrations were not seen in clams up-estuary (maximum of 1.92 µg g −1 ) from these sites and were reduced down-estuary (maximum of 2.67 µg g −1 ). Silver is not common naturally in the environment, so its elevated presence is usually indicative of anthropogenic influences such as municipal and industrial discharge. Monthly sampling of reproductive status of clams characterized the reproductive cycle and differences in the patterns of reproductive activity that corresponded to changes in Ag tissue concentrations. The proportion of reproductive clams was less than 60% during periods when tissue concentrations were high (generally >2 µg g −1 ). When tissue concentrations of Ag decreased (≤1 µg g −1 ), the proportion of reproductive clams was 80 to 100%. A comparison between the annual proportion of reproductive clams and annual Ag tissue concentrations showed a significant negative correlation. No other measured environmental variables were correlated with reproductive impairment. The weight-of-evidence approach strongly supports a cause and effect relationship between Ag contamination and reduced reproductive activity in P. amurensis .

California↗