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USGS2001

Shallow ground-water quality beneath rice areas in the Sacramento Valley, California, 1997

In 1997, the U.S. Geological Survey installed and sampled 28 wells in rice areas in the Sacramento Valley as part of the National Water-Quality Assessment Program. The purpose of the study was to assess the shallow ground-water quality and to determine whether any effects on water quality could be related to human activities and particularly rice agriculture. The wells installed and sampled were between 8.8 and 15.2 meters deep, and water levels were between 0.4 and 8.0 meters below land surface. Ground-water samples were analyzed for 6 field measurements, 29 inorganic constituents, 6 nutrient constituents, dissolved organic carbon, 86 pesticides, tritium (hydrogen- 3), deuterium (hydrogen-2), and oxygen-18. At least one health-related state or federal drinking-water standard (maximum contaminant or long-term health advisory level) was exceeded in 25 percent of the wells for barium, boron, cadmium, molybdenum, or sulfate. At least one state or federal secondary maximum contaminant level was exceeded in 79 percent of the wells for chloride, iron, manganese, specific conductance, or dissolved solids. Nitrate and nitrite were detected at concentrations below state and federal 2000 drinking-water standards; three wells had nitrate concentrations greater than 3 milligrams per liter, a level that may indicate impact from human activities. Ground-water redox conditions were anoxic in 26 out of 28 wells sampled (93 percent). Eleven pesticides and one pesticide degradation product were detected in ground-water samples. Four of the detected pesticides are or have been used on rice crops in the Sacramento Valley (bentazon, carbofuran, molinate, and thiobencarb). Pesticides were detected in 89 percent of the wells sampled, and rice pesticides were detected in 82 percent of the wells sampled. The most frequently detected pesticide was the rice herbicide bentazon, detected in 20 out of 28 wells (71 percent); the other pesticides detected have been used for rice, agricultural, and non-agricultural purposes. All pesticide concentrations were below state and federal 2000 drinking-water standards. The relation of the ground-water quality to natural processes and human activities was tested using statistical methods (Spearman rank correlation, Kruskal?Wallis, or rank-sum tests) to determine whether an influence from rice land-use or other human activities on ground-water chemistry could be identified. The detection of pesticides in 89 percent of the wells sampled indicates that human activities have affected shallow ground-water quality. Concentrations of dissolved solids and inorganic constituents that exceeded state or federal 2000 drinking-water standards showed a statistical relation to geomorphic unit. This is interpreted as a relation to natural processes and variations in geology in the Sacramento River Basin; the high concentrations of dissolved solids and most inorganic constituents did not appear to be related to rice land use. No correlation was found between nitrate concentration and pesticide occurrence, indicating that an absence of high nitrate concentrations is not a predictor of an absence of pesticide contamination in areas with reducing ground-water conditions in the Sacramento Valley. Tritium concentrations, pesticide detections, stable isotope data, and dissolved-solids concentrations suggest that shallow ground water in the ricegrowing areas of the Sacramento Valley is a mix of recently recharged ground water containing pesticides, nitrate, and tritium, and unknown sources of water that contains high concentrations of dissolved solids and some inorganic constituents and is enriched in oxygen-18. Evaporation of applied irrigation water, which leaves behind salt, accounts for some of the elevated concentrations of dissolved solids. More work needs to be done to understand the connections between the land surface, shallow ground water, deep ground water, and the drinking-water supplies in the Sacramento Valley.

Water-Resources Investigations Report↗

USGS2012

Applications of mineral surface chemistry to environmental problems

Environmental surface chemistry involves processes that occur at the interface between the regolith, hydrosphere and atmosphere. The more limited scope of the present review addresses natural and anthropogenically-induced inorganic geochemical reactions between solutes in surface and ground waters and soil and aquifer substrates. Important surficial reactions include sorption, ion exchange, dissolution, precipitation and heterogeneous oxidation/reduction processes occurring at the solid/aqueous interface. Recent research advances in this field have addressed, both directly and indirectly, societal issues related to water quality, pollution, biogeochemical cycling, nutrient budgets and chemical weathering related to long term global climate change. This review will include recent advances in the fundamental and theoretical understanding of these surficial processes, breakthroughs in experimental and instrumental surface characterization, and development of methodologies for field applications.

Reviews of Geophysics↗

USGS1996

Episodic acidification of small streams in the northeastern United states: Effects on fish populations

As part of the Episodic Response Project (ERP), we studied the effects of episodic acidification on fish in 13 small streams in the northeastern United States: four streams in the Adirondack region of New York, four streams in the Catskills, New York, and five streams in the northern Appalachian Plateau, Pennsylvania. In situ bioassays with brook trout (Salvelinus fontinalis) and a forage fish species (blacknose dace (Rhinichthys atratulus), mottled sculpin (Cottus bairdi), or slimy sculpin (Cottus cognatus), depending on the region) measured direct toxicity. Movements of individual brook trout, in relation to stream chemistry, were monitored using radiotelemetry. Electrofishing surveys assessed fish community status and the density and biomass of brook trout in each stream. During low flow, all streams except one had chemical conditions considered suitable for the survival and reproduction of most fish species (median pH 6.0-7.2 during low flow; inorganic Al < 60 μg/L). ERP streams with suitable conditions during low flow, but moderate-to-severe episodic acidification during high flow, had higher fish mortality in bioassays, net down-stream movement of brook trout during events, and lower brook trout density and biomass compared to nonacidic streams, and lacked acid-sensitive fish species (blacknose dace and sculpin). Movement of trout into refugia (areas with higher pH and lower Al) during episodes partially mitigated the adverse effects of episodes. Recolonization from alkaline tributaries or microhabitats can maintain low densities of fish in streams that experience severe acidic episodes, but it is not sufficient to sustain fish densities and community composition at levels expected in the absence of these episodes. Fish responses to acid-base chemistry were fairly consistent across regions. In general, trout abundance was reduced and acid-sensitive fish species were absent from ERP streams with median pH < 5.0-5.2 during high flow and inorganic Al > 100-200 μg/L. We conclude that episodic acidification can have long-term effects on fish communities in small streams.

Ecological Applications↗

USGS2016

Dragonfly Mercury Project—A citizen science driven approach to linking surface-water chemistry and landscape characteristics to biosentinels on a national scale

Mercury is a globally distributed pollutant that threatens human and ecosystem health. Even protected areas, such as national parks, are subjected to mercury contamination because it is delivered through atmospheric deposition, often after long-range transport. In aquatic ecosystems, certain environmental conditions can promote microbial processes that convert inorganic mercury to an organic form (methylmercury). Methylmercury biomagnifies through food webs and is a potent neurotoxicant and endocrine disruptor. The U.S. Geological Survey (USGS), the University of Maine, and the National Park Service (NPS) Air Resources Division are working in partnership at more than 50 national parks across the United States, and with citizen scientists as key participants in data collection, to develop dragonfly nymphs as biosentinels for mercury in aquatic food webs. To validate the use of these biosentinels, and gain a better understanding of the connection between biotic and abiotic pools of mercury, this project also includes collection of landscape data and surface-water chemistry including mercury, methylmercury, pH, sulfate, and dissolved organic carbon and sediment mercury concentration. Because of the wide geographic scope of the research, the project also provides a nationwide “snapshot” of mercury in primarily undeveloped watersheds.

Fact Sheet↗

USGS1998

Recovery and validation of historical sediment quality data from coastal and estuarine areas: An integrated approach

A comprehensive database of sediment chemistry and environmental parameters has been compiled for Boston Harbor and Massachusetts Bay. This work illustrates methodologies for rescuing and validating sediment data from heterogeneous historical sources. It greatly expands spatial and temporal data coverage of estuarine and coastal sediments. The database contains about 3500 samples containing inorganic chemical, organic, texture and other environmental data dating from 1955 to 1994. Cooperation with local and federal agencies as well as universities was essential in locating and screening documents for the database. More than 80% of references utilized came from sources with limited distribution (gray literature). Task sharing was facilitated by a comprehensive and clearly defined data dictionary for sediments. It also served as a data entry template and flat file format for data processing and as a basis for interpretation and graphical illustration. Standard QA/QC protocols are usually inapplicable to historical sediment data. In this work outliers and data quality problems were identified by batch screening techniques that also provide visualizations of data relationships and geochemical affinities. No data were excluded, but qualifying comments warn users of problem data. For Boston Harbor, the proportion of irreparable or seriously questioned data was remarkably small (<5%), although concentration values for metals and organic contaminants spanned 3 orders of magnitude for many elements or compounds. Data from the historical database provide alternatives to dated cores for measuring changes in surficial sediment contamination level with time. The data indicate that spatial inhomogeneity in harbor environments can be large with respect to sediment-hosted contaminants. Boston Inner Harbor surficial sediments showed decreases in concentrations of Cu, Hg, and Zn of 40 to 60% over a 17-year period.A comprehensive database of sediment chemistry and environmental parameters has been compiled for Boston Harbor and Massachusetts Bay. This work illustrates methodologies for rescuing and validating sediment data from heterogeneous historical sources. It greatly expands spatial and temporal data coverage of estuarine and coastal sediments. The database contains about 3500 samples containing inorganic chemical, organic, texture and other environmental data dating from 1995 to 1994. Cooperation with local and federal agencies as well as universities was essential in locating and screening documents for the database. More than 80% of references utilized came from sources with limited distribution (gray Task sharing was facilitated by a comprehensive and clearly defined data dictionary for sediments. It also served as a data entry template and flat file format for data processing and as a basis for interpretation and graphical illustration. Standard QA/QC protocols are usually inapplicable to historical sediment data. In this work outliers and data quality problems were identified by batch screening techniques that also provide visualizations of data relationships and geochemical affinities. No data were excluded, but qualifying comments warn users of problem data. For Boston Harbor, the proportion of irreparable or seriously questioned data was remarkably small (<5%), although concentration values for metals and organic contaminants spanned 3 orders of magnitude for many elements or compounds. Data from the historical database provide alternatives to dated cores for measuring changes in surficial sediment contamination level with time. The data indicate that spatial inhomogeneity in harbor environments can be large with respect to sediment-hosted contaminants. Boston Inner Harbor surficial sediments showed decreases in concentrations Cu, Hg, and Zn of 40 to 60% over a 17-year period.

Massachusetts↗

USGS2008

Assessing sulfate reduction and methane cycling in a high salinity pore water system in the northern Gulf of Mexico

Pore waters extracted from 18 piston cores obtained on and near a salt-cored bathymetric high in Keathley Canyon lease block 151 in the northern Gulf of Mexico contain elevated concentrations of chloride (up to 838 mM) and have pore water chemical concentration profiles that exhibit extensive departures (concavity) from steady-state (linear) diffusive equilibrium with depth. Minimum ??13C dissolved inorganic carbon (DIC) values of -55.9??? to -64.8??? at the sulfate-methane transition (SMT) strongly suggest active anaerobic oxidation of methane (AOM) throughout the study region. However, the nonlinear pore water chemistry-depth profiles make it impossible to determine the vertical extent of active AOM or the potential role of alternate sulfate reduction pathways. Here we utilize the conservative (non-reactive) nature of dissolved chloride to differentiate the effects of biogeochemical activity (e.g., AOM and/or organoclastic sulfate reduction) relative to physical mixing in high salinity Keathley Canyon sediments. In most cases, the DIC and sulfate concentrations in pore waters are consistent with a conservative mixing model that uses chloride concentrations at the seafloor and the SMT as endmembers. Conservative mixing of pore water constituents implies that an undetermined physical process is primarily responsible for the nonlinearity of the pore water-depth profiles. In limited cases where the sulfate and DIC concentrations deviated from conservative mixing between the seafloor and SMT, the ??13C-DIC mixing diagrams suggest that the excess DIC is produced from a 13C-depleted source that could only be accounted for by microbial methane, the dominant form of methane identified during this study. We conclude that AOM is the most prevalent sink for sulfate and that it occurs primarily at the SMT at this Keathley Canyon site.

Marine and Petroleum Geology↗

USGS2013

Use of soil-streamwater relationships to assess regional patterns of acidic deposition effects in the northeastern USA

Declines of acidic deposition levels by as much as 50% since 1990 have led to partial recovery of surface waters in the northeastern USA but continued depletion of soil calcium through this same period suggests a disconnection between soil and surface water chemistry. To investigate the role of soil-surface water interactions in recovery from acidification, the first regional survey to directly relate soil chemistry to stream chemistry during high flow was implemented in a 4144-km 2 area of the Catskill region of New York, where acidic deposition levels are among the highest in the East. More than 40% of 95 streams sampled in the southern Catskill Mountains were determined to be acidified and had inorganic monomeric aluminum concentrations that exceeded a threshold that is toxic to aquatic biota. More than 80% likely exceeded this threshold during the highest flows, but less than 10% of more than 100 streams sampled were acidified in the northwestern portion of the region. Median Oa horizon soil base saturation ranged from 50% to 80% at 200 sites across the region, but median base saturation in the upper 10 cm of the B horizon was less than 20% across the region and was only 2% in the southern area. Aluminum is likely to be interfering with root uptake of calcium in the mineral horizon in approximately half the sampled watersheds. Stream chemistry was highly variable over the Catskill region and, therefore, did not always reflect the calcium depletion of the B horizon that our sampling suggested was nearly ubiquitous throughout the region. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

New York↗

USGS1983

Crassulacean acid metabolism in the seasonally submerged aquatic Isoetes howellii

Evidence to date is consistent with the hypothesis that the submerged aquatic Isoetes howellii Engelmann possesses crassulacean acid metabolism. Quantitative 14 C uptake studies indicate that CO 2 assimilation in both the light and dark are functions of pH and total inorganic carbon level. In both the light and dark, maximum uptake rates in 0.6 mM NaHCO 3 were double the rates in 0.3 mM NaHCO 3 . At both carbon levels there was a large drop in carbon assimilation rate between pH 6 and 8. In nature water pH and inorganic carbon level fluctuated diurnally thus complicating the determination of the contribution of light vs dark CO 2 uptake to the total carbon gain. On a sunny day between 0600 and 1200 h water chemistry changed markedly with ∼40% reduction in total carbon, ∼2 pH unit rise resulting from ∼100% depletion of free CO 2 . Under such conditions daytime deacidification in Isoetes leaves was 88% complete by noon. In contrast, on an overcast day, reduction of carbon in the water was much slower, deacidification was only 46% complete by noon and substantial malic acid levels remained in the leaves at the end of the day. Upon emergence crassulacean acid metabolism was largely lost in Isoetes leaves. Preliminary estimates suggest that under natural submerged conditions, early morning photosynthetic rates may be substantially higher than dark CO 2 uptake rates, though uptake rates throughout much of the day could be substantially lower than nightime CO 2 assimilation.

Oecologia↗

USGS2022

Sedimentary organics in Glen Torridon, Gale Crater, Mars: Results from the SAM instrument suite and supporting laboratory analyses

The Sample Analysis at Mars (SAM) suite instrument on board NASA's Curiosity rover has characterized the inorganic and organic chemical composition of seven samples from the Glen Torridon (GT) clay-bearing unit. A variety of organic molecules were detected with SAM using pyrolysis (up to ∼850°C) and wet chemistry experiments coupled with evolved gas analysis (EGA) and gas chromatography-mass spectrometry. SAM EGA and GCMS analyses revealed a greater diversity and abundance of sulfur-bearing aliphatic and aromatic organic compounds in the sediments of this Gale crater unit than earlier in the mission. We also report the detection of nitrogen-containing, oxygen-containing, and chlorine-containing molecules, as well as polycyclic aromatic hydrocarbons found in GT, although the sources of some of these organics may be related to the presence of chemical reagents in the SAM instrument background. However, sulfur-bearing organics released at high temperature (≥600°C) are likely derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources and consistent with the presence of recalcitrant organic materials in the sample. The SAM measurements of the GT clay-bearing unit expand the inventory of organic matter present in Gale crater and is also consistent with the hypothesis that clay minerals played an important role in the preservation of ancient refractory organic matter on Mars. These findings deepen our understanding of the past habitability and biological potential of Gale crater.

JGR Planets↗

USGS2021

Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model

Widely used isotope ratio mass spectrometers have limited capabilities to measure metabolites, drugs, or small polyatomic ions without the loss of structural isotopic information. A new approach has recently been introduced that uses electrospray ionization Orbitrap to measure multidimensional isotope signatures of intact polar compounds. Using nitrate as a model compound, this study aims to establish performance metrics for comparisons with conventional IRMS at the natural abundance level. We present a framework on how to convert isotopolog intensities to δ values that are commonly used in the isotope geochemistry community. The quantification of seven nitrate isotopologs provides multiple pathways for obtaining the primary N and O δ values including non-mass-dependent O isotope variations, as well as opportunities to explore nonrandom isotopic distributions (i.e., clumping effects) within molecular nitrate. Using automation and the adaptation of measurement principles that are specific to isotope ratio analysis, nitrate δ15NAIR, δ18OVSMOW, and δ17OVSMOW were measured with a long-term precision of 0.4‰ or better for isotopic reference materials and purified nitrate from environmental samples. In addition, we demonstrate promising results for unpurified environmental samples in liquid form. With these new developments, this study connects the two largely disparate mass spectrometry fields of bioanalytical MS and isotope ratio MS, thus providing a route to measure new isotopic signatures in diverse organic and inorganic solutes.

Analytical Chemistry↗

USGS1994

Humic and fulvic acids: sink or source in the availability of metals to the marine bivalves Macoma balthica and Potamocorbula amurensis ?

Humic acids (HA) and fulvic acids (FA) are common forms of organic matter in marine sediments, and are routinely ingested by deposit- and suspension-feeding animals. These compounds may be a sink for metals, implying that once metals are bound to humic substances they are no longer available to food webs. A series of experiments was conducted to quantitatively examine this premise using 2 estuarine bivalves from San Francisco Bay, USA: the suspension feeder Potarnocorbula arnurensis and the facultative deposit feeder Macoma balthica . HA and FA, isolated from marine sediments, were bound as organic coatings to either hydrous ferric oxides (HFO) or silica particles. Cd and Cr(II1) were adsorbed to the organic coatings or directly to uncoated HFO and silica particles. Pulse-chase laboratory feeding expenments using 109 Cd and 51 Cr(III) were then conducted to determine absorption efficiencies of Cd and Cr for individual specimens using each of the particle types. The results demonstrated that: (1) absorption of Cr(I1I) from all types of non-living particles was consistently low (< 11%). Ingested Cd showed greater bioavailability than Cr(IIl), perhaps due to differences in metal chemistry. (2) Bivalves absorbed Cd bound to uncoated HFO or silica particles (i.e. with no HA or FA present). (3) The presence of organic coatings on particles reduced Cd bioavailabhty compared with uncoated particles. (4) Both geochemical and biological conditions affected the food chain transfer of Cd. The data suggest that in marine systems inorganic and organic-coated particles are predominantly a sink for Cr in sediments. In the transfer of Cd to consumer animals, inorganic particles and humic substances can act as a link (although not a highly efficient one) under oxidized conditions.

Marine Ecology Progress Series↗

USGS2019

Response of water chemistry and young-of-year brook trout to channel and watershed liming in streams showing lagging recovery from acidic deposition

Reductions in sulfur emissions have initiated chemical recovery of surface waters impacted by acidic deposition in the Adirondack region of New York State. However, acidified streams remain common in the region, which limits recovery of brook trout ( Salvelinus fontinalis ) populations. To investigate liming as a method to accelerate recovery of brook trout, the channels of two acidified streams were limed annually from 2012 to 2015, and an entire watershed of a third acidified tributary was limed by helicopter in 2013. Stream flow, water chemistry, and density of young-of-year (YOY) brook trout were measured in limed streams, an untreated acidified stream, and a buffered reference stream. Lime additions increased pH and acid-neutralizing capacity and decreased inorganic monomeric aluminum concentrations to less than 2.0 μmol/L, the minimum concentration at which in situ brook trout mortality has been documented. However, of the two channel-limed streams, only stream T8 showed a significant response (P < 0.01) in YOY density, increasing from a mean of 0.4 fish/m2 before liming to 2.7 fish/m2 after liming. No YOY brook trout response was observed in the stream within the limed watershed. Groundwater inputs to streams were identified by relative differences in temperature and concentrations of silica and sodium. YOY brook trout densities increased only in the channel-limed stream (T8) with suitable groundwater inputs for fall spawning and a summer nursery. Results suggest that targeted liming of acidified streams with the necessary groundwater habitat could be beneficial in accelerating recovery of brook trout populations.

New York↗

USGS2010

Coupled hydrology and biogeochemistry of Paleocene–Eocene coal beds, northern Gulf of Mexico

Thirty-six formation waters, gas, and microbial samples were collected and analyzed from natural gas and oil wells producing from the Paleocene to Eocene Wilcox Group coal beds and adjacent sandstones in north-central Louisiana, USA, to investigate the role hydrology plays on the generation and distribution of microbial methane. Major ion chemistry and Cl − Br relations of Wilcox Group formation waters suggest mixing of freshwater with halite-derived brines. High alkalinities (up to 47.8 meq/L), no detectable SO 4 , and elevated δ 13 C values of dissolved inorganic carbon (up to 20.5‰ Vienna Peedee belemnite [VPDB]) and CO 2 (up to 17.67‰ VPDB) in the Wilcox Group coals and adjacent sandstones indicate the dominance of microbial methanogenesis. The δ 13 C and δD values of CH 4 , and carbon isotope fractionation of CO 2 and CH 4 , suggest CO 2 reduction is the major methanogenic pathway. Geochemical indicators for methanogenesis drop off significantly at chloride concentrations above ∼1.7 mol/L, suggesting that high salinities inhibit microbial activity at depths greater than ∼1.6 km. Formation waters in the Wilcox Group contain up to 1.6% modern carbon (A 14 C) to at least 1690 m depth; the covariance of δD values of co-produced H 2 O and CH 4 indicate that the microbial methane was generated in situ with these Late Pleistocene or younger waters. The most enriched carbon isotope values for dissolved inorganic carbon (DIC) and CO 2 , and highest alkalinities, were detected in Wilcox Group sandstone reservoirs that were CO 2 flooded in the 1980s for enhanced oil recovery, leading to the intriguing hypothesis that CO 2 sequestration may actually enhance methanogenesis in organic-rich formations.

GSA Bulletin↗

USGS2017

The response of soil and stream chemistry to decreases in acid deposition in the Catskill Mountains, New York, USA

The Catskill Mountains have been adversely impacted by decades of acid deposition, however, since the early 1990s, levels have decreased sharply as a result of decreases in emissions of sulfur dioxide and nitrogen oxides. This study examines trends in acid deposition, stream-water chemistry, and soil chemistry in the southeastern Catskill Mountains. We measured significant reductions in acid deposition and improvement in stream-water quality in 5 streams included in this study from 1992 to 2014. The largest, most significant trends were for sulfate (SO 4 2− ) concentrations (mean trend of −2.5 μeq L −1 yr −1 ); hydrogen ion (H + ) and inorganic monomeric aluminum (Al im ) also decreased significantly (mean trends of −0.3 μeq L −1 yr −1 for H + and −0.1 μeq L −1 yr −1 for Al im for the 3 most acidic sites). Acid neutralizing capacity (ANC) increased by a mean of 0.65 μeq L −1 yr −1 for all 5 sites, which was 4 fold less than the decrease in SO 4 2− concentrations. These upward trends in ANC were limited by coincident decreases in base cations (−1.3 μeq L −1 yr −1 for calcium + magnesium). No significant trends were detected in stream-water nitrate (NO 3 − ) concentrations despite significant decreasing trends in NO 3 − wet deposition. We measured no recovery in soil chemistry which we attributed to an initially low soil buffering capacity that has been further depleted by decades of acid deposition. Tightly coupled decreasing trends in stream-water silicon (Si) (−0.2 μeq L −1 yr −1 ) and base cations suggest a decrease in the soil mineral weathering rate. We hypothesize that a decrease in the ionic strength of soil water and shallow groundwater may be the principal driver of this apparent decrease in the weathering rate. A decreasing weathering rate would help to explain the slow recovery of stream pH and ANC as well as that of soil base cations.

New York↗

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↗

USGS2009

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry↗

USGS2001

Effect of canopy removal on snowpack quantity and quality, fraser experimental forest, Colorado

Snowpack peak water equivalent (PWE), ion concentration, content, and spatial distribution of ion load data from spring 1987-1996 in a 1 ha clearcut and adjacent forested plots vegetated by mature Picea engelmannii and Abies lasiocarpa in the Fraser experimental forest (FEF), Colorado are presented. Our objectives were: (1) to see if a forest opening might redistribute snowfall, snowpack moisture, and snowpack chemical content, and (2) to examine the importance of canopy interception on snowpack quantity and chemistry. On an average, the canopy intercepted 36% of snowfall. Interception was correlated with snowfall amount, snowpack PWE beneath the canopy, and air temperature. Canopy removal increased snowpack PWE to >90% cumulative snowfall inputs. Snowpack K-, H-, and NH4+ concentrations on the clearcut were lower and NO3- higher than in the snowpack beneath the forested plots. Cu mulative snowfall K+ input was less than in the clearcut snowpack; H+ inputs were greater in snowfall than in the snowpack of any plot; and inorganic N (NO3- and NH4+) inputs from snowfall to the clearcut were greater than to the forested plots. Processes accounting for the differences between snowfall inputs and snowpack ion content were leaching of organic debris in the snowpack, differential elution of the snowpack, and canopy retention. There were significant trends by year in snowpack ion content at PWE without similar trends in snowfall inputs. This finding coupled with snowpack ion elution bring into question the use of snowpack chemistry as an indicator of winter atmospheric inputs in short-term studies. ?? 2001 Elsevier Science B.V.

Journal of Hydrology↗

USGS2021

Modeling the bioavailability of nickel and zinc to Ceriodaphnia dubia and Neocloeon triangulifer in toxicity tests with Natural Waters

We studied biotic ligand model (BLM) predictions of toxicity of nickel (Ni) and zinc (Zn) in natural waters from Illinois and Minnesota USA which had combinations of pH, hardness, and dissolved organic carbon (DOC) more extreme than 99.7% of waters in a nationwide database. We conducted 7-d chronic tests with Ceriodaphnia dubia, and 96-hr acute test and 14-d chronic tests with Neocloeon triangulifer, and estimated LC50s and EC20s for both species. Toxicity of Ni and Zn to both species differed among test waters by factors from 8 (Zn tests with C. dubia ) to 35 (Zn tests with N. triangulifer ). For both species and metals, tests with Minnesota waters (low pH and hardness, high DOC) showed lower toxicity than Illinois waters (high pH, high hardness, low DOC). Recalibration of the Ni BLM to be more responsive to pH-related changes improved predictions of Ni toxicity, especially for C. dubia . We compared several input data scenarios for the Zn BLM, which generally had minor effects on Model Performance Scores (MPS). A scenario that included inputs of modeled dissolved inorganic carbon and measured Al and Fe(III) produced highest MPS values for tests with both C. dubia and N. triangulifer . Overall, the BLM framework successfully modeled variation in toxicity for both Zn and Ni across wide ranges of water chemistry in tests with both standard and novel test organisms.

Illinois, Minnesota↗