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At least 253 records · Page 14Linked to original sources

Temporal evaluation of estrogenic endocrine disruption markers in smallmouth bass (Micropterus dolomieu) reveals seasonal variability in intersex

A reconnaissance project completed in 2009 identified intersex and elevated plasma vitellogenin in male smallmouth bass inhabiting the Missisquoi River, VT. In an attempt to identify the presence and seasonality of putative endocrine disrupting chemicals or other factors associated with these observations, a comprehensive reevaluation was conducted between September 2012 and June 2014. Here, we collected smallmouth bass from three physically partitioned reaches along the river to measure biomarkers of estrogenic endocrine disruption in smallmouth bass. In addition, polar organic chemical integrative samples (POCIS) were deployed to identify specific chemicals associated with biological observations. We did not observe biological differences across reaches indicating the absence of clear point source contributions to the observation of intersex. Interestingly, intersex prevalence and severity decreased in a stepwise manner over the timespan of the project. Intersex decreased from 92.8% to 28.1%. The only significant predictor of intersex prevalence was year of capture, based on logistic regression analysis. The mixed model of fish length and year-of-capture best predicted intersex severity. Intersex severity was also significantly different across late summer and early spring collections indicating seasonal changes in this metric. Plasma vitellogenin and liver vitellogenin Aa transcript abundance in males did not indicate exposure to estrogenic endocrine disrupting chemicals at any of the four sample collections. Analysis of chemicals captured by the POCIS as well as results of screening discrete water samples or POCIS extracts did not indicate the contribution of appreciable estrogenic chemicals. It is possible that unreported changes in land-use activity have ameliorated the problem, and our observations indicate recovery. Regardless, this work clearly emphasizes that single, snap shot sampling for intersex may not yield representative data given that the manifestation of this condition within a population can change dramatically over time.

Vermont

Biological and mineralogical controls over cycling of low molecular weight organic compounds along a soil chronosequence

Low molecular weight organic compounds (LMWOC) represent a small but critical component of soil organic matter (SOM) for microbial growth and metabolism. The fate of these compounds is largely under microbial control, yet outside the cell, intrinsic soil properties can also significantly influence their turnover and retention. Using a chronosequence representing 1200 ka of pedogenic development, we compared physicochemical vs biological controls on the turnover and retention of fast-cycling carbon (C), e.g. glucose (GLU) and p-hydroxybenzoic acid (PHBA). Along the chronosequence, we observed mineralogical gradients whereby amorphous constituents were greatest in intermediate-aged sites, while older sites demonstrated soils with more ordered and less reactive mineralogy. Soil microbial community composition varied along the soil chronosequence and we observed reductions in total biomass and fungal biomass from younger to older sites, but this did not affect the turnover of LMWOC. Microbial utilization of LMWOC was substrate- and soil-dependent; amorphous Fe and Al oxides reduced the respiration of PHBA but respiration from glucose remained less affected. Variation in soil mineralogy did not significantly alter recovery of PHBA within microbial biomass or fungal vs. bacterial biomarkers, suggesting that reduced respiration of the phenolic resulted from direct mineral interaction with ionizable functional groups rather than changes to microbial allocation of PHBA. We conclude patterns of soil carbon storage observed across chronosequences are moderated by mineralogical effects on microbial access to LMWOC, independent of variation in microbial community composition. Keywords: 13C; Glucose; Microbial biomass C; Organo-mineral interactions; p-Hydroxybenzoic acid; Selective dissolution mineralogical analyses

Soil Biology and Biochemistry

Longitudinal evaluation of leukocyte transcripts in killer whales ( Orcinus Orca )

Early identification of illness and/or presence of environmental and/or social stressors in free-ranging and domestic cetaceans is a priority for marine mammal health care professionals. Incorporation of leukocyte gene transcript analysis into the diagnostic tool kit has the potential to augment classical diagnostics based upon ease of sample storage and shipment, inducible nature and well-defined roles of transcription and associated downstream actions. Development of biomarkers that could serve to identify “insults” and potentially differentiate disease etiology would be of great diagnostic value. To this end, a modest number of peripheral blood leukocyte gene transcripts were selected for application to a domestic killer whale population with a focus on broad representation of inducible immunologically relevant genes. Normalized leukocyte transcript values, longitudinally acquired from 232 blood samples derived from 26 clinically healthy whales, were not visibly influenced temporally nor by sex or the specific Park in which they resided. Stability in leukocyte transcript number during periods of health enhances their potential use in diagnostics through identification of outliers. Transcript levels of two cytokine genes, IL-4 and IL-17, were highly variable within the group as compared to the other transcripts. IL-4 transcripts were typically absent. Analysis of transcript levels on the other genes of interest, on an individual animal basis, identified more outliers than were visible when analyzed in the context of the entire population. The majority of outliers (9 samples) were low, though elevated transcripts were identified for IL-17 from 2 animals and one each for Cox-2 and IL-10. The low number of outliers was not unexpected as sample selection was intentionally directed towards animals that were clinically healthy at the time of collection. Outliers may reflect animals experiencing subclinical disease that is transient and self-limiting. The immunologic knowledge derived from longitudinal immunologic studies in killer whales, as was the target of the present study, has the potential to improve diagnostics and health related decision making for this and other domestic and free-ranging cetacean species.

Veterinary Immunology and Immunopathology

Effects of the environmental estrogenic contaminants bisphenol A and 17α-ethinyl estradiol on sexual development and adult behaviors in aquatic wildlife species

Endocrine disrupting chemicals ( EDCs ), including the mass-produced component of plastics, bisphenol A (BPA) are widely prevalent in aquatic and terrestrial habitats. Many aquatic species, such as fish, amphibians, aquatic reptiles and mammals, are exposed daily to high concentrations of BPA and ethinyl estradiol (EE2), estrogen in birth control pills. In this review, we will predominantly focus on BPA and EE2, well-described estrogenic EDCs. First, the evidence that BPA and EE2 are detectable in almost all bodies of water will be discussed. We will consider how BPA affects sexual and neural development in these species, as these effects have been the best characterized across taxa. For instance, such chemicals have been in many cases reported to cause sex-reversal of males to females. Even if these chemicals do not overtly alter the gonadal sex, there are indications that several EDCs might demasculinize male-specific behaviors that are essential for attracting a mate. In so doing, these chemicals may reduce the likelihood that these males reproduce. If exposed males do reproduce, the concern is that they will then be passing on compromised genetic fitness to their offspring and transmitting potential transgenerational effects through their sperm epigenome . We will thus consider how diverse epigenetic changes might be a unifying mechanism of how BPA and EE2 disrupt several processes across species. Such changes might also serve as universal species diagnostic biomarkers of BPA and other EDCs exposure. Lastly, the evidence that estrogenic EDCs-induced effects in aquatic species might translate to humans will be considered.

General and Comparative Endocrinology

Developmental exposure to bisphenol A (BPA) alters sexual differentiation in painted turtles (Chrysemys picta)

Environmental chemicals can disrupt endocrine signaling and adversely impact sexual differentiation in wildlife. Bisphenol A (BPA) is an estrogenic chemical commonly found in a variety of habitats. In this study, we used painted turtles ( Chrysemys picta ), which have temperature-dependent sex determination (TSD), as an animal model for ontogenetic endocrine disruption by BPA. We hypothesized that BPA would override TSD and disrupt sexual development. We incubated farm-raised turtle eggs at the male-producing temperature (26 °C), randomly assigned individuals to treatment groups: control, vehicle control, 17β-estradiol (E2, 20 ng/g-egg) or 0.01, 1.0, 100 μg BPA/g-egg and harvested tissues at hatch. Typical female gonads were present in 89% of the E2-treated “males”, but in none of the control males ( n = 35). Gonads of BPA-exposed turtles had varying amounts of ovarian-like cortical (OLC) tissue and disorganized testicular tubules in the medulla. Although the percentage of males with OLCs increased with BPA dose (BPA-low = 30%, BPA-medium = 33%, BPA-high = 39%), this difference was not significant ( p = 0.85). In all three BPA treatments, SOX9 patterns revealed disorganized medullary testicular tubules and β-catenin expression in a thickened cortex. Liver vitellogenin , a female-specific liver protein commonly used as an exposure biomarker , was not induced by any of the treatments. Notably, these results suggest that developmental exposure to BPA disrupts sexual differentiation in painted turtles. Further examination is necessary to determine the underlying mechanisms of sex reversal in reptiles and how these translate to EDC exposure in wild populations.

General and Comparative Endocrinology

Evidence and characteristics of hydrolytic disproportionation of organic matter during metasomatic processes

Petroleum-geochemical analyses of carbonaceous regionally metamorphosed rocks, carbonaceous rocks from ore deposits, and alkalic plutonic rocks from diverse settings, demonstrated the presence of very low to moderately low concentrations of solvent-extractable organic matter, this observation in spite of the fact that some of these rocks were exposed to extremely high metamorphic temperatures. Biomarker and ??13C analyses established that the extractable organic matter originated as sedimentary-derived hydrocarbons. However, the chemistry of the extractable bitumen has been fundamentally transformed from that found in sediment bitumen and oils. Asphaltenes and resins, as defined in the normal petroleum-geochemical sense, are completely missing. The principal aromatic hydrocarbons present in oils and sediment bitumens (especially the methylated naphthalenes) are either in highly reduced concentrations or are missing altogether, Instead, aromatic hydrocarbons typical of sediment bitumens and oils are very minor, and a number of unidentified compounds and oxygen-bearing compounds are dominant. Relatively high concentrations of alkylated benzenes are typical. The polar "resin" fraction, eluted during column chromatography, is the principal compound group, by weight, being composed of six to eight dominant peaks present in all samples, despite the great geologic diversity of the samples. These, and other, observations suggest that a strong drive towards equilibrium exists in the "bitumen." Gas chromatograms of the saturated hydrocarbons commonly have a pronounced hump in both the n-paraffins and naphthenes, centered near the C19 to C26 carbon numbers, and a ubiquitos minimum in the n-paraffin distribution near n-C12 to n-C14. Multiple considerations dictate that the bitumen in the samples is indigenous and did not originate from either surficial field contamination or from laboratory procedures. Our observations are consistent with the hydrolytic disproportion of organic matter (HDOM), in which water and organic matter, including hydrocarbons, easily exchange hydrogen or oxygen with one another under certain conditions (Helgeson et al., 1993). The process appears to take place via well-known organic-chemical redox reaction pathways and is most evident in open-fluid systems. The conclusion that HDOM took place in the analyzed samples, thus producing the chemistry of the extractable bitumen, is supported by numerous previously published organic-geochemical studies of metamorphic, volcanic, plutonic, and ore-deposit-related rocks by other investigators. HDOM is suggested as an unrecognized geologic agent of fundamental importance. The process appears to control major chemical reactions in diverse geologic environments including, but not limited to, petroleum geology and geochemistry, regional metamorphism, and base- and precious-metal ore deposition. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310–381°C), time (12–144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil–hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330°C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ≈ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381°C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350°C for 72 h, or 330°C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115°C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers (“molecular fossils”) that are less susceptible to hydrogen exchange with water-derived hydrogen.

Geochimica et Cosmochimica Acta

Comparison of pigeon guillemot, Cepphus columba, blood parameters from oiled and unoiled areas of Alaska eight years after the Exxon Valdez oil spill

In 1997, we compared the haematological and plasma biochemical profiles among populations of pigeon guillemots, Cepphus columba, in areas oiled and not oiled by the 1989 Exxon Valdez oil spill (EVOS) that occurred in Prince William Sound (PWS), Alaska. Pigeon guillemot populations in PWS were injured by EVOS and have not returned to pre-spill levels. If oil contamination is limiting recovery of pigeon guillemots in PWS, then we expected that blood parameters of pigeon guillemots would differ between oiled and unoiled areas and that these differences would be consistent with either toxic responses or lower fitness. We collected blood samples from chicks at approximately 20 and 30 days after hatching. Physiological changes associated with chick growth were noted in several blood parameters. We found that only calcium and mean cell volume were significantly different between the chicks in oiled and unoiled areas. Despite these differences, blood biomarkers provided little evidence of continuing oil injury to pigeon guillemot chicks, eight years after the EVOS. Preliminary data from adults indicated elevated aspartate aminotransferase activity in the adults from the oiled area, which is consistent with hepatocellular injury. Because adults have greater opportunities for exposure to residual oil than nestlings, we recommend studies that fully evaluate the health of adults residing in oiled areas. (C) 2000 Elsevier Science Ltd.

Marine Pollution Bulletin

Geochemical evidence for mudstone as the possible major oil source rock in the Jurassic Turpan Basin, Northwest China

Geologists and geochemists have debated whether hydrocarbons from Jurassic coal measures are derived from the mudstones or the coals themselves. This paper identifies mudstones as the possible major source rock of hydrocarbons in the Jurassic basins in Northwest China. The Turpan Basin is used as a representative model. Mudstones in the Middle-Lower Jurassic are very well developed in the basin and have an average genetic potential from 2 to 4 mg/g. The vitrinite reflectance of the source rocks ranges from 0.6 to 1.3%, exhibiting sufficient thermal maturity to generate oil and gas. Biomarkers in crude oils from the basin are similar to those in mudstones from the coal-bearing strata, with a low tricyclic terpane (cheilanthane) content, a relatively high content of low carbon number (less than C22) tricyclic terpanes and a low content of high carbon number tricyclic terpanes, relatively high ratios of Ts/Tm, and C29 Ts/17?? (H)-C29 norhopane, and low ratios of Tm/17?? (H)-C30 hopane and 17?? (H)-C31 homohopane/17?? (H)-C30 hopane. These characteristics and the distribution of steranes and terpanes in the crude oil and mudstone differ significantly from those of the Jurassic coals and carbonaceous shales of the basin, indicating mudstone is possibly the major source rock of the oils in the Turpan Basin. ?? 2001 Elsevier Science Ltd. All rights reserved.

Organic Geochemistry

Early developments in petroleum geochemistry

Petroleum geochemistry is the outgrowth of the application of the principles and methods of organic chemistry to petroleum refining and petroleum geology . This paper reviews 120 years of petroleum geochemistry, from about 1860 to 1980, and includes a discussion of the formal recognition of petroleum geochemistry as an earth-science discipline starting in 1959 when a general petroleum geochemistry symposium was first organized at Fordham University, New York. A chronology of significant events, including concepts, techniques, and textbook publications, is presented. Because petroleum geochemistry has been a tool for petroleum exploration from the beginning, the early developments of surface prospecting, source-rock identification, and oil/oil and oil/source correlation are discussed, along with the application of geochemistry to petroleum migration, accumulation, and alteration. In addition the paper deals with the biomarker revolution, which began in earnest about 1964, and with early models of geothermal history. Concepts in petroleum geochemistry have continually evolved, enhanced by the development of new analytical techniques, leading to new discoveries concerning the origin and occurrence of petroleum.

Organic Geochemistry

Organic geochemistry and petrology of oil source rocks, Carpathian Overthrust region, southeastern Poland - Implications for petroleum generation

The organic mailer rich Oligocene Menilite black shales and mudstones are widely distributed in the Carpathian Overthrust region of southeastern Poland and have excellent hydrocarbon generation potential, according to TOC, Rock-Eval, and petrographic data. Extractable organic matter was characterized by an equable distribution of steranes by carbon number, by varying amounts of 28,30-dinor-hopane, 18??(H)-oleanane and by a distinctive group of C24 ring-A degraded triterpanes. The Menilite samples ranged in maturity from pre-generative to mid-oil window levels, with the most mature in the southeastern portion of the study area. Carpathian petroleum samples from Campanian Oligocene sandstone reservoirs were similar in biomarker composition to the Menilite rock extracts. Similarities in aliphatic and aromatic hydrocarbon distributions between petroleum asphaltene and source rock pyrolyzates provided further evidence genetically linking Menilite kerogens with Carpathian oils.

Organic Geochemistry

Geochemistry of coastal tarballs in southern California—A tribute to I. R. Kaplan

In the southern offshore California borderland, natural oil seeps occur mainly in the Santa Barbara Channel and Santa Monica Bay. Coastal tar residues (tarballs) from beaches bordering these water bodies were analyzed for six geochemical parameters: stable carbon isotopic compositions (δ 13 C) and four biomarker ratios (C 28 IC 29 hopane, sterane/hopane, refractory index, bisnorhopane index), and the presence or absence of trisnorhopane. The objectives of this study were to group these residues and infer possible sources and transport directions. Three major groups were established. Two groups are likely from natural seeps near the Channel Islands, whereas the third group probably comes from seeps within Santa Monica Bay. Residues from all groups occur on the Channel Islands and on mainland beaches from as far south as San Diego to Point Reyes north of San Francisco.

California

An “EAR” on environmental surveillance and monitoring: A case study on the use of Exposure–Activity Ratios (EARs) to prioritize sites, chemicals, and bioactivities of concern in Great Lakes waters

Current environmental monitoring approaches focus primarily on chemical occurrence. However, based on concentration alone, it can be difficult to identify which compounds may be of toxicological concern and should be prioritized for further monitoring, in-depth testing, or management. This can be problematic because toxicological characterization is lacking for many emerging contaminants. New sources of high-throughput screening (HTS) data, such as the ToxCast database, which contains information for over 9000 compounds screened through up to 1100 bioassays, are now available. Integrated analysis of chemical occurrence data with HTS data offers new opportunities to prioritize chemicals, sites, or biological effects for further investigation based on concentrations detected in the environment linked to relative potencies in pathway-based bioassays. As a case study, chemical occurrence data from a 2012 study in the Great Lakes Basin along with the ToxCast effects database were used to calculate exposure–activity ratios (EARs) as a prioritization tool. Technical considerations of data processing and use of the ToxCast database are presented and discussed. EAR prioritization identified multiple sites, biological pathways, and chemicals that warrant further investigation. Prioritized bioactivities from the EAR analysis were linked to discrete adverse outcome pathways to identify potential adverse outcomes and biomarkers for use in subsequent monitoring efforts.

Great Lakes

Exposure to human-associated chemical markers of fecal contamination and self-reported illness among swimmers at recreational beaches

Anthropogenic chemicals have been proposed as potential markers of human fecal contamination in recreational water. However, to date, there are no published studies describing their relationships with illness risks. Using a cohort of swimmers at seven U.S. beaches, we examined potential associations between the presence of chemical markers of human fecal pollution and self-reported gastrointestinal (GI) illness, diarrhea, and respiratory illness. Swimmers were surveyed about their beach activities, water exposure, and baseline symptoms on the day of their beach visit, and about any illness experienced 10–12 days later. Risk differences were estimated using model-based standardization and adjusted for the swimmer’s age, beach site, sand contact, rainfall, and water temperature. Sixty-two chemical markers were analyzed from daily water samples at freshwater and marine beaches. Of those, 20 were found consistently. With the possible exception of bisphenol A and cholesterol, no chemicals were consistently associated with increased risks of illness. These two chemicals were suggestively associated with 2% and 1% increased risks of GI illness and diarrhea in both freshwater and marine beaches. Additional research using the more sensitive analytic methods currently available for a wider suite of analytes is needed to support the use of chemical biomarkers to quantify illness risk and identify fecal pollution sources.

Alabama, Indiana, Michigan, Mississippi, Ohio, Rho

Quantifying depuration of methylmercury from fish consumption by travelers

During a two-week field sampling expedition in Gabon, two American scientists consumed fish daily from the Ogooué River watershed. We sampled their scalp and facial hair periodically to evaluate hair as a biomarker to track shifts in methylmercury (MeHg) exposure from diet. Each individual differed in the onset and extent of MeHg accumulation but showed similar depuration rates. Pretrip baseline Hg isotope values between participants were distinct from Gabonese fishes allowing us to detect shifts in MeHg sources in the hair of both individuals. δ 202 Hg values tracked the mass-dependent fractionation of MeHg depuration stemming from in vivo metabolism, leading to δ 202 Hg increases of 0.014 ± 0.001 per mille and total Hg losses of 8.3 ± 1.1 ng g –1 daily. While limited in scope due to minimal participants, our findings reveal a complex interaction between prior MeHg burdens, contemporary MeHg intakes, and sources of consumed fishes (locally caught versus market-sourced) in determining the dynamics of MeHg concentrations and δ 202 Hg in human hair. We also suggest that the offset in δ 202 Hg values used in literature between fish and human hair (1.75 ± 0.25‰) may overlook a time domain that increases starting fish-hair δ 202 Hg offsets (0.94‰), through time.

Agence Nationale des Parcs Nationaux

Contaminant exposure and effects: Terrestrial vertebrates database: Trends and data gaps for Atlantic Coast estuaries

In order to examine the condition of biota in Atlantic coast estuaries, "Contaminant Exposure and Effects—Terrestrial Vertebrates" database (CEE-TV) has been compiled through computerized search of published literature, review of existing databases, and solicitation of unpublished reports from conservation agencies, private groups, and universities. Summary information has been entered into the database, including species, collection date (1965–present), site coordinates, estuary name, hydrologic unit code, sample matrix, contaminant concentrations, biomarker and bioindicator responses, and reference source, utilizing a 98-field character and numeric format. Currently, the CEE-TV database contains 3699 geo-referenced records representing 190 vertebrate species and >140,000 individuals residing in estuaries from Maine through Florida. This relational database can be directly queried or imported into a Geographic Information System to examine spatial patterns, identify data gaps and areas of concern, generate hypotheses, and focus ecotoxicological field assessments. Information on birds made up the vast majority (83%) of the database, with only a modicum of data on amphibians (<0.1%). Of the >75,000 chemical compounds in commerce, only 118 commonly measured environmental contaminants were quantified in tissues of terrestrial vertebrates. There were no CEE-TV data records in 15 of the 67 estuaries located along the Atlantic coast and Florida Gulf coast. The CEE-TV database has a number of potential applications including focusing biomonitoring efforts to generate critically needed ecotoxicological data in the numerous "gaps" along the coast, reducing uncertainty about contaminant risk, identifying areas for mitigation, restoration or special management, and ranking ecological conditions of estuaries.

Environmental Monitoring and Assessment

Inhibition of erythrocytes δ-aminolevulinic acid dehydratase (ALAD) activity in fish from waters affected by lead smelters

We assessed the effects on fish of lead (Pb) released to streamsby smelters located in Trail, BC (Canada), E. Helena, MT, Herculaneum, MO, and Glover, MO. Fish were collected by electrofishing from sites located downstream of smelters and from reference sites. Blood from each fish was analyzed for &delta;-aminolevulinic acid dehydratase ( ALAD ) activity and hemoglobin (Hb), and samples of blood, liver, or carcass were analyzed for Pb, zinc (Zn), or both. Fish collected downstreamof all four smelters sites had elevated Pb concentrations, decreased ALAD activity, or both relative to their respectivereference sites. At E. Helena, fish from the downstream site also had lower Hb concentrations than fish from upstream. Differences among taxa were also apparent. Consistent with previous studies, ALAD activity in catostomids ( Pisces : Catostomidae-northern hog sucker, Hypentelium nigricans ;river carpsucker, Carpiodes carpio ; largescale sucker, Catostomus macrocheilus ; and mountain sucker, C. platyrhynchus ) seemed more sensitive to Pb-induced ALAD inhibition than the salmonids ( Pisces : Salmonidae-rainbow trout, Oncorhynchus mykiss ; brook trout, Salvelinus fontinalis ) or common carp ( Cyprinus carpio ). Some of these differences may have resulted from differential accumulation of Zn, which was not measured at all sites. We detected no ALAD activity in channel catfish ( Ictaluruspunctatus ) from either site on the Mississippi River at Herculaneum, MO. Our findings confirmed that Pb is releasedto aquatic ecosystems by smelters and accumulated by fish, andwe documented potentially adverse effects of Pb in fish. We recommend that Zn be measured along with Pb when ALAD activityis used as a biomarker and the collection of at least 10 fish ofa species at each site to facilitate statistical analysis.

Environmental Monitoring and Assessment

Fluorescence-based proxies for lignin in freshwater dissolved organic matter

Lignin phenols have proven to be powerful biomarkers in environmental studies; however, the complexity of lignin analysis limits the number of samples and thus spatial and temporal resolution in any given study. In contrast, spectrophotometric characterization of dissolved organic matter (DOM) is rapid, noninvasive, relatively inexpensive, requires small sample volumes, and can even be measured in situ to capture fine-scale temporal and spatial detail of DOM cycling. Here we present a series of cross-validated Partial Least Squares models that use fluorescence properties of DOM to explain up to 91% of lignin compositional and concentration variability in samples collected seasonally over 2 years in the Sacramento River/San Joaquin River Delta in California, United States. These models were subsequently used to predict lignin composition and concentration from fluorescence measurements collected during a diurnal study in the San Joaquin River. While modeled lignin composition remained largely unchanged over the diurnal cycle, changes in modeled lignin concentrations were much greater than expected and indicate that the sensitivity of fluorescence-based proxies for lignin may prove invaluable as a tool for selecting the most informative samples for detailed lignin characterization. With adequate calibration, similar models could be used to significantly expand our ability to study sources and processing of DOM in complex surface water systems.

Journal of Geophysical Research G: Biogeosciences