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Bias and precision of selected analytes reported by the National Atmospheric Deposition Program and National Trends Network, 1984

The U.S. Geological Survey operated a blind audit sample program during 1974 to test the effects of the sample handling and shipping procedures used by the National Atmospheric Deposition Program and National Trends Network on the quality of wet deposition data produced by the combined networks. Blind audit samples, which were dilutions of standard reference water samples, were submitted by network site operators to the central analytical laboratory disguised as actual wet deposition samples. Results from the analyses of blind audit samples were used to calculate estimates of analyte bias associated with all network wet deposition samples analyzed in 1984 and to estimate analyte precision. Concentration differences between double blind samples that were submitted to the central analytical laboratory and separate analyses of aliquots of those blind audit samples that had not undergone network sample handling and shipping were used to calculate analyte masses that apparently were added to each blind audit sample by routine network handling and shipping procedures. These calculated masses indicated statistically significant biases for magnesium, sodium , potassium, chloride, and sulfate. Median calculated masses were 41.4 micrograms (ug) for calcium, 14.9 ug for magnesium, 23.3 ug for sodium, 0.7 ug for potassium, 16.5 ug for chloride and 55.3 ug for sulfate. Analyte precision was estimated using two different sets of replicate measures performed by the central analytical laboratory. Estimated standard deviations were similar to those previously reported. (Author 's abstract)

Water-Resources Investigations Report↗

Estimation of streamflow characteristics and assessment of trends in the Niobrara River at Mariaville, Nebraska

A computer model was used to synthesize a long-term streamflow record for the Niobrara River at Mariaville, Nebraska. The record was developed on the basis of 30-plus years of streamflow data from 3 upstream sites, and the U. S. Geological Survey 's CONROUT model was calibrated using 294 days of measured flow at Mariaville; for the calibration period, 87% of the synthesized daily discharges were within 15% of the measured values. The synthesized record was analyzed for trends in streamflow characteristics. A marked decrease in the average consecutive-day, low-flow discharges was detected after 1964, ranging between 162 cu ft/sec less for the 1-day low flow and 200 cu ft/sec less for the 14-day low flow. The decrease probably was caused by the start-up of operations at Merritt Reservoir. (Author 's abstract)

Water-Resources Investigations Report↗

Results of external quality-assurance program for the National Atmospheric Deposition Program and National Trends Network during 1985

External quality assurance monitoring of the National Atmospheric Deposition Program (NADP) and National Trends Network (NTN) was performed by the U.S. Geological Survey during 1985. The monitoring consisted of three primary programs: (1) an intersite comparison program designed to assess the precision and accuracy of onsite pH and specific conductance measurements made by NADP and NTN site operators; (2) a blind audit sample program designed to assess the effect of routine field handling on the precision and bias of NADP and NTN wet deposition data; and (3) an interlaboratory comparison program designed to compare analytical data from the laboratory processing NADP and NTN samples with data produced by other laboratories routinely analyzing wet deposition samples and to provide estimates of individual laboratory precision. An average of 94% of the site operators participated in the four voluntary intersite comparisons during 1985. A larger percentage of participating site operators met the accuracy goal for specific conductance measurements (average, 87%) than for pH measurements (average, 67%). Overall precision was dependent on the actual specific conductance of the test solution and independent of the pH of the test solution. Data for the blind audit sample program indicated slight positive biases resulting from routine field handling for all analytes except specific conductance. These biases were not large enough to be significant for most data users. Data for the blind audit sample program also indicated that decreases in hydrogen ion concentration were accompanied by decreases in specific conductance. Precision estimates derived from the blind audit sample program indicate that the major source of uncertainty in wet deposition data is the routine field handling that each wet deposition sample receives. Results of the interlaboratory comparison program were similar to results of previous years ' evaluations, indicating that the participating laboratories produced comparable data when they analyzed identical wet deposition samples, and that the laboratory processing NADP and NTN samples achieved the best analyte precision of the participating laboratories. (Author 's abstract)

Water-Resources Investigations Report↗

External quality-assurance results for the National Atmospheric Deposition Program and the National Trends Network during 1986

During 1986, the U.S. Geological Survey operated three programs to provide external quality-assurance monitoring of the National Atmospheric Deposition Program and National Trends Network. An intersite-comparison program was used to assess the accuracy of onsite pH and specific-conductance determinations at quarterly intervals. The blind-audit program was used to assess the effect of routine sample handling on the precision and bias of program and network wet-deposition data. Analytical results from four laboratories, which routinely analyze wet-deposition samples, were examined to determine if differences existed between laboratory analytical results and to provide estimates of the analytical precision of each laboratory. An average of 78 and 89 percent of the site operators participating in the intersite-comparison met the network goals for pH and specific conductance. A comparison of analytical values versus actual values for samples submitted as part of the blind-audit program indicated that analytical values were slightly but significantly (a = 0.01) larger than actual values for pH, magnesium, sodium, and sulfate; analytical values for specific conductance were slightly less than actual values. The decreased precision in the analyses of blind-audit samples when compared to interlaboratory studies indicates that a large amount of uncertainty in network deposition data may be a result of routine field operations. The results of the interlaboratory comparison study indicated that the magnitude of the difference between laboratory analyses was small for all analytes. Analyses of deionized, distilled water blanks by participating laboratories indicated that the laboratories had difficulty measuring analyte concentrations near their reported detection limits. (USGS)

Water-Resources Investigations Report↗

Estimated use of water in North Dakota in 1985 and trends during 1960-85

Estimates of water use in North Dakota have been compiled by the U.S. Geological Survey every 5 years since 1950. These estimates have been published in national summaries of water use (MacKichan, 1951, 1957; MacKichan and Kammerer, 1961; Murray, 1968; Murrary and Reeves, 1972, 1977; and Solley and others, 1983, 1987). In this report, estimates of offstream water use for 1985 and trends in water use in 5-year increments from 1960 through 1985 are presented for the following categories of use: Public supply Domestic and commercial Industrial and mining Thermoelectric power Agricultural (irrigation and nonirrigation)

North Dakota↗

External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network during 1991

The U.S. Geological Survey used four programs in 1991 to provide external quality assurance for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN). An intersite-comparison program was used to evaluate onsite pH and specific-conductance determinations. The effects of routine sample handling, processing, and shipping of wet-deposition samples on analyte determinations and an estimated precision of analyte values and concentrations were evaluated in the blind-audit program. Differences between analytical results and an estimate of the analytical precision of four laboratories routinely measuring wet deposition were determined by an interlaboratory-comparison program. Overall precision estimates for the precipitation-monitoring system were determined for selected sites by a collocated-sampler program. Results of the intersite-comparison program indicated that 93 and 86 percent of the site operators met the NADP/NTN accuracy goal for pH determinations during the two intersite-comparison studies completed during 1991. The results also indicated that 96 and 97 percent of the site operators met the NADP/NTN accuracy goal for specific-conductance determinations during the two 1991 studies. The effects of routine sample handling, processing, and shipping, determined in the blind-audit program indicated significant positive bias (a=.O 1) for calcium, magnesium, sodium, potassium, chloride, nitrate, and sulfate. Significant negative bias (or=.01) was determined for hydrogen ion and specific conductance. Only ammonium determinations were not biased. A Kruskal-Wallis test indicated that there were no significant (*3t=.01) differences in analytical results from the four laboratories participating in the interlaboratory-comparison program. Results from the collocated-sampler program indicated the median relative error for cation concentration and deposition exceeded eight percent at most sites, whereas the median relative error for sample volume, sulfate, and nitrate concentration at all sites was less than four percent. The median relative error for hydrogen ion concentration and deposition ranged from 4.6 to 18.3 percent at the four sites and as indicated in previous years of the study, was inversely proportional to the acidity of the precipitation at a given site. Overall, collocated-sampling error typically was five times that of laboratory error estimates for most analytes.

Water-Resources Investigations Report↗

Ground-water quality and trends at two industrial wastewater-injection sites in northwestern Florida, 1975-91

Industrial wastewater from two synthetic-fiber manufacturing plants has been injected into the Lower Floridan aquifer near Pensacola, Florida, since 1963, and near Milton, Florida, since 1975. Trend analysis of selected water-quality characteristics in water from four monitoring wells at each of these plants indicates that injected wastewater has affected ground-water quality in the Lower Floridan aquifer, which contains nonpotable water, up to 1.5 miles from the injection wells at the plant near Pensacola and at least 0.3 mile from the injection wells at the plant near Milton. No evidence for upward seepage of injected wastewater through the overlying Bucatunna Clay to the Upper Floridan aquifer was found at either of the plants.

Florida↗

Land use, organochlorine compound concentrations, and trends in benthic-invertebrate communities in selected stream basins in Chester County, Pennsylvania

Land use was analyzed for the drainage areas of 26 stream sites in Chester County, Pa., that cover a total area of 227 square miles or about 30 percent of the country. The most significant land-use changes during 1967-87 were decreased agricultural land use, increased residential land use, and increased commercial and industrial land use. Bulk samples of stream-bottom materials were collected at 42 sites in the study area from October 1985 through November 1987 and analyzed for content of organochlorine pesticides and polychlorinated biphenyls (PCB's). Organochlorine compounds and (or) PCB's were detected in streambed materials collected at 40 of the 42 sites sampled. The most enriched compounds (greater than 15 micrograms per kilogram) were PCB's, chlordane, and DDT plus its breakdown products. Data suggest that chlordane residues are closely associated with residential land use. PCB residues are closely associated with industrial and commercial land use. Cores of labeled sediments from the site of Icedale Lake, a drained reservoir on the West Branch Brandywine Creek, indicate that DDT was the first organochlorine pesticide to enter the Brandywine Creek; concentrations peaked in the late 1940's and early 1950's. As DDT influx subsequently decreased, influxes of chlordane and dieldrin increased and peaked in the mind-1960's, before the Chester County biological monitoring program. Influx of all pesticides appears to have decreased significantly since the 1960's. Contingency analyses showed that the relation between the Kendall slope estimator for trend and the increases in residential land use of 12 percent or greater were significant at the 95-percent confidence level. The contingency tables also showed that the relation between diversity indices of less than 2.25 and organochlorine-compound concentrations greater than 45 micrograms per kilogram was significant at the 95-percent confidence level.

Water-Resources Investigations Report↗

Nutrient and suspended-sediment concentrations, trends, loads, and yields from the nontidal part of the Susquehanna, Potomac, Patuxent, and Choptank rivers, 1985-96

The Chesapeake Bay River-Input Monitoring Program was established to characterize the water quality of four major rivers in Maryland, and to quantify the load and the long-term trends in concentrations of nutrients (nitrogen and phosphorus) and suspended sediment transported from the nontidal part of each river to the Chesapeake Bay. As part of the River-Input Monitoring Program, nutrient and suspended-sediment data and streamflow data were collected from 1985 through 1996 at the Susquehanna, Potomac, Patuxent, and Choptank Rivers above the points of tidal influence. The data were used to determine the effectiveness of strategies aimed at reducing nutrients entering Chesapeake Bay from its tributaries. Of the four rivers studied, the Patuxent River had the highest median concentrations of total nitrogen (2.6 milligrams per liter), total phosphorus (0.17 milligrams per liter), and suspended sediment (45 milligrams per liter) during the 12-year period. From 1985?96, flow-adjusted concentrations of total nitrogen decreased in all but the Potomac River, flow-adjusted concentrations of total phosphorus decreased in all four rivers, and flow-adjusted concentrations of suspended sediment decreased in all but the Susquehanna River. The rivers that contributed the greatest amount of streamflow to Chesapeake Bay, the Susquehanna and Potomac, also contributed the greatest nutrient loads and suspended-sediment loads to the Bay. The Susquehanna River transported the highest average-annual loads of total phosphorus (4.7 million pounds per year) and total nitrogen (146 million pounds per year), while the Potomac River transported the highest average-annual load of suspended sediment (4.1 billion pounds per year) to the Bay. Annual loads and annual mean streamflow were normalized by basin drainage area to account for some of the hydrologic differences among the river basins. An increase in precipitation from south to north is still apparent, however, when comparing the water yields among river basins. The Susquehanna River Basin had the highest median annual water yield during the study period; the other three basins all had similar water yields. The Susquehanna River and the Patuxent River had the highest median annual yields of nitrogen during the study period. The Patuxent River also had the highest median annual yield of total phosphorus during the study period, while the Potomac River had the highest median yield of suspended sediment. Annual yields of total phosphorus and suspended sediment from the Susquehanna and the Choptank River Basins are lower than those from the Potomac and Patuxent River Basins. These relatively small yields from the Susquehanna River may be due to the location of the sampling station below Conowingo Dam. A series of three dams upstream trap a large percentage of sediment and total phosphorus carried by the Susquehanna River to Chesapeake Bay.

Delaware, Maryland, New Jersey, New York, Pennsylv↗

External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network, 1995-96

The U.S. Geological Survey operated four external quality-assurance programs for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) in 1995 and 1996: the intersite-comparison program, the blind-audit program, the interlaboratory- comparison program, and the collocated-sampler program. The intersite-comparison program assessed the precision and bias of pH and specific-conductance determinations made by NADP/NTN site operators. The analytical bias introduced during routine handling, processing, and shipping of wet-deposition samples and precision of analyte values was estimated using a blind-audit program. An interlaboratory-comparison program was used to evaluate differences between analytical results and to estimate the analytical precision of five North American laboratories that routinely analyzed wet deposition. A collocated-sampler program estimated the precision of the overall precipitation collection and analysis system from initial sample collection through final storage of the data. Results of two intersite-comparison studies completed in 1995 indicated 94.6 and 94.4 percent of the onsite pH determinations met the NADP/NTN accuracy goals, whereas 97.2 and 98.3 percent of the specific-conductance determinations were within the established limits. The percentages of onsite determinations that met the accuracy goals in 1996 were slightly less for both pH and specific-conductance than in 1995. In 1996, 93.2 and 87.5 percent of onsite pH determinations met the accuracy goals, whereas the percentage of onsite specific-conductance measurements that met the goals was 93.9 and 94.9 percent.The blind audit program utilizes a paired sample design to evaluate the effects of routine sample handling, processing and shipping on the chemistry of weekly precipitation samples. The portion of the blind audit sample subject to all of the normal onsite handling and processing steps of a regular weekly precipitation sample is referred to as the bucket portion, whereas the portion receiving only minimal handling is referred to as the bottle portion. Throughout the report, the term positive bias in regard to blind-audit results indicates that the bucket portion had a higher concentration than the bottle portion. The paired t-test of 1995 blind-audit data indicated that routine sample handling, processing, and shipping introduced a very small positive bias (a=0.05) for hydrogen ion and specific conductance and a slight negative bias (a =0.05) for ammonium and sodium. In 1995, the median paired differences between the bucket and bottle portions ranged from -0.02 milligram per liter for both ammonium and nitrate to +0.002 milligram per liter for calcium. Although the paired t-test indicated a very small positive bias for hydrogen ion, the median paired difference between the bucket and bottle portions was 0.00 microequivalents per liter, whereas for specific conductance, the median paired difference between the bucket and bottle portions was 0.200 microsiemens per centimeter in 1995. The paired t-test of blind-audit results in 1996 indicated statistically significant bias for 6 of the 10 analytes. Only chloride, nitrate, hydrogen ion, and specific conductance were not biased in 1996. However, the magnitude of the bias in 1996 was very small and only of limited importance from the viewpoint of an analytical chemist or data user. The median paired differences between the bucket and bottle portions ranged from -0.02 milligram per liter for both ammonium and chloride to +0.006 milligram per liter for calcium. For hydrogen ion, the median paired difference between the bucket and bottle portions was -0.357 microequivalent per liter; for specific conductance, the median paired difference between the bucket and bottle portions was 0.00 microsiemens per centimeter in 1996. Surface-chemistry effects due to different amounts of precipitation contacting the sample collection and shipping container surfac

Water-Resources Investigations Report↗

Water resources of Monroe County, New York, water years 1989-93, with emphasis on water quality in the Irondequoit Creek basin: Part 2. Atmospheric deposition, ground water, streamflow, trends in water quality, and chemical loads to Irondequoit Bay

Irondequoit Creek, which drains 169 square miles in the eastern part of Monroe County, has been recognized as a source of contaminants that contribute to the eutrophication of Irondequoit Bay on Lake Ontario. The discharge from sewage-treatment plants to the creek and its tributaries was eliminated in 1979 by diversion to another wastewater-treatment facility, but sediment and nonpoint-source pollution remain a concern. This report presents data from five surface-water sites in the Irondequoit Creek basin. Irondequoit Creek at Railroad Mills, East Branch Allen Creek, Allen Creek near Rochester, Irondequoit Creek at Blossom Road, and Irondequoit Creek at Empire Boulevard, to supplement published data from 1984-88. Data from Northrup Creek, which drains 11.7 square miles in western Monroe County, provide information on surface-water quality west of the Genesee River. Also presented are water-level and water-quality data from 12 observation-well sites in Ellison and Powdermill Parks and atmospheric-deposition data from 1 site (Mendon Ponds). Concentrations of several chemical constituents in streams of the Irondequoit Creek basin showed statistically significant trends during 1989-93. Concentrations of total suspended-solids and volatile suspended-solids in Irondequoit Creek at Blossom Road decreased 13.5 and 12.5 percent per year, respectively, and those at Empire Boulevard decreased 33.5 and 22 percent per year, respectively. Concentrations of ammonia plus organic nitrogen increased 17.6 percent per year at one site in the basin, but decreased 8.5 and 22.3 percent per year at two sites. Nitrite plus nitrate decreased at only one site (3.5 percent per year). Concentrations of total phosphorus increased at two sites (about 7 percent per year) and decreased at two other sites (7.6 and 29.9 percent per year), and orthophosphate concentrations increased at one site (10.8 percent per year). Dissolved chloride increased at three sites (1.7 to 10.9 percent per year), and dissolved sulfate decreased at one site (2.1 percent per year) and increased at one site (6.8 percent per year). Median concentrations of constituents were significantly lower in atmospheric deposition than in streamflow, although annual deposition of ammonia nitrogen, nitrite plus nitrate, total phosphorus, and orthophosphate in the basin exceeded the amounts removed by streamflow. Atmospheric deposition of chloride and sulfate, by contrast, represented only 1 and 12 percent, respectively, of the loads transported by Irondequoit Creek (Blossom Road site). Comparison of water-quality data from the Allen Creek site and Irondequoit Creek at Blossom Road from water years 1989-93 with corresponding data from 1984-88 indicates significant changes in median concentrations of several constituents. The concentration of dissolved chloride increased at Blossom Road and was unchanged at Allen Creek, whereas sulfate decreased at both sites. Concentrations of ammonia plus organic nitrogen, and nitrite plus nitrate, were significantly lower during 1989-93 than during 1984-88 at both sites. Total phosphorus concentration was lower during 1984-88 than during 1989-93 at Blossom Road but showed no change at Allen Creek, and orthophosphate concentration for 1989-93 was lower than in 1984-88 at both sites. Comparison of chemical loads in atmospheric deposition also indicates significant changes in many constituents. Five-year-mean loads of sodium, sulfate, and lead in atmospheric deposition for 1989-93 exceeded those for 1984-88, whereas 5-year-mean loads of calcium, magnesium, potassium, chloride, nitrite plus nitrate, ammonia nitrogen, and orthophosphate for 1989-93 were lower than in 1984-88. The changes in surface-water quality resulted from several factors within the basin, including land-use changes, annual and seasonal variations in streamflow, and year-to-year variations in the application of deicing salts on area roads. Statistical analyses of long-term (9 years or more) flow records of three unregulated streams in Monroe County indicate that annual mean flows for water years 1989- 93 were in the normal range (20th- to 80th-percentile). The greatest mean annual flow in this period-about 140 percent of normal at Irondequoit Creek and Black Creek-occurred in 1993, but the annual mean flow for that water year at Allen Creek was only 98 percent of normal. The lowest annual mean flows of these streams-ranging from 75 percent of normal to 93 percent of normal-occurred in 1989. The average annual mean flows for these streams for 1989-93 was 104 percent of normal, and that for 1984-88 was normal.

New York↗

Water quality of North Carolina streams – Water-quality characteristics for selected sites on the Cape Fear River, North Carolina, 1955-80 – Variability, loads, and trends of selected constituents

Historical water-quality data collected by the U.S. Geological Survey from the Cape Fear River at Lock 1, near Kelly, North Carolina, show increasing concentrations of total-dissolved solids, specific conductance, sulfate, chloride, nitrite plus nitrate nitrogen, magnesium, sodium, and potassium during the past 25 years. Silica and pH show decreasing trends during the same 1957-80 period. These long-term changes in water quality are statistically related to increasing population in the basin and especially to manufacturing employment. Comparisons of water-quality data for present conditions with estimated natural conditions indicate that over 50 percent of the loads of most major dissolved substances in the river at Lock 1 are the result of development impacts in the basin. Over 80 percent of the nutrients plus nitrate nitrogen, ammonia nitrogen, and total phosphorus presently in the streams originate from development. At four sampling stations on the Cape Fear River and its tributaries, recent water-quality data show that most constituents are always within North Carolina water-quality standards and Environmental Protection Agency water-quality criteria. However, iron, manganese and mercury concentrations usually exceed standards.

North Carolina↗

Amphibian chytrid prevalence on boreal toads in SE Alaska and NW British Columbia: Tests of habitat, life stages, and temporal trends

Tracking and understanding variation in pathogens such as Batrachochytrium dendrobatidis ([Bd]), which causes amphibian chytridiomycosis and has caused population declines globally, is a priority for many land managers. However, there has been relatively little sampling of amphibian communities at high latitudes. We used skin swabs collected during 2005–2017 from boreal toads (Anaxyrus boreas; N = 248), in southeast Alaska (USA; primarily in Klondike Gold Rush National Historical Park [KLGO]) and northwest British Columbia (Canada) to determine how Bd prevalence varied across life stages, habitat characteristics, local species richness, and time. Across all years, Bd prevalence peaked in June and was >3 times greater for adult toads (37.5%) vs. juveniles and metamorphs (11.2%). Bd prevalence for toads in the KLGO area, where other amphibian species are rare or absent, was highest from river habitats (55.0%), followed by human-modified upland wetlands (32.3%) and natural upland wetlands (12.7%) — the same rank-order these habitats are used for toad breeding. No Columbia spotted frogs (N = 12) or wood frogs (N = 2) from the study area tested Bd-positive, although all were from an area of low host density where Bd has not been detected. Prevalence of Bd on toads in the KLGO area decreased during 2005–2015. This trend from a largely single-species system may be encouraging or concerning, depending on how Bd is affecting vital rates, and emphasizes the need to understand effects of pathogens before translating disease prevalence into management actions.

Southeastern Alaska, Northwestern British Columbia↗

Embryo deformities and nesting trends in Kemp’s ridley sea turtles Lepidochelys kempii before and after the Deepwater Horizon oil spill

Kemp’s ridley sea turtles Lepidochelys kempii were disproportionately affected by the Deepwater Horizon (DWH) oil spill, which began on 20 April 2010. Embryo deformities were documented in inviable L. kempii eggs before (2008-2010) and after (2011-2013) the DWH spill in 2 Texas (USA) nesting areas (Upper Texas Coast and Padre Island National Seashore). Additional nesting trends, including clutch size and hatching success, were also investigated. Total and late-stage embryo deformity prevalence were 1.5 times greater after 2010 than before, but low in all nesting seasons (mean ± SD: 0.7 ± 8.5% total; 0.6 ± 8.0% late-stage) and did not differ between locations. Craniofacial and carapace deformities were the most frequently observed deformity types. Documented nests in both areas declined in 2010 relative to previous years, ending an exponential increase observed beginning in 1995. Clutch size remained consistent before and after the spill. Hatching success averaged 87.0 ± 33.3% in all years, but no effects from DWH were determined. Collectively, these data represent useful benchmarks against which to judge impacts of future crude oil spills and other catastrophic events.

Texas↗

Benthic sulfate reduction along the Chesapeake Bay central channel. I. Spatial trends and controls

Factors controlling the spatial distribution of benthic sulfate reduction (SR) were investigated at 3 stations [upper (UB), mid (MB) and lower bay (LB)] along the Chesapeake Bay (eastern USA) central channel from early spring through late fall, 1989 to 1994. Annual rates of 0 to 12 cm depth-integrated SR were 0.96, 9.62 and 6.33 mol S m-2 yr-1 for UB, MB and LB, respectively, as calculated from 35SO42- incubations. SR was carbon limited at UB, LB, and at the sediment surface at MB, and SO42- limited at depth at MB. Temperature explained 33 to 68% of the variability in annual rates, with an apparent influence on SR which increased in the seaward direction in surface sediments. We speculate that the enhanced response of SR to temperature in LB surface sediments was linked to seasonal variations in macrofaunal activity associated with temperature. Estimates of reduced-S burial indicated that only 4 to 8% of sulfur reduced annually was buried as Fe-S minerals at MB and LB, with the remainder presumably being reoxidized. In contrast, >50% of the sulfur reduced annually was buried at UB, due to comparatively low SR rates and the high concentration of reactive iron in the oligohaline region. SR mineralized 18 to 32% of the annual primary production. Our results indicate that organic quality may be more important than the absolute quantity of organic loading in dictating the magnitude of benthic SR rates along an estuarine gradient. Spatial trends in SR reflected the combined influence of deposited organic matter quality and quantity, SO42- availability, the presence or absence of benthic macrofauna, overlying water dissolved O2 conditions, reduced-S reoxidation dynamics, and iron-sulfide mineral formation.

Marine Ecology Progress Series↗

Region-wide trends of nesting ospreys in northwestern Mexico: a three-decade perspective

We used a double-sampling technique (air plus ground survey) in 2006, with partial double coverage, to estimate the present size of the Osprey (Pandion haliaetus) nesting population in northwestern Mexico (coastal Baja California, islands in the Gulf of California, and coastal Sonora and Sinaloa). With the exception of Natividad, Cedros, and San Benitos islands along the Pacific coast of Baja California (all three excluded from our coverage in 2006 due to fog), this survey was a repeat of previous surveys conducted by us with the same protocol in 1977 and 1992/1993, allowing for estimates of regional population trends. The minimum population estimate for the area we surveyed in 2006 was 1343 nesting pairs, an 81% increase since 1977, but only a 3% increase since 1992/1993. The population on the Gulf side of Baja California generally remained stable during the three surveys (255, 236, and 252 pairs, respectively). The population of the Midriff Islands (Gulf of California in the vicinity of 29°N latitude) remained similar from 1992/1993 (308 pairs) to 2006 (289 pairs), but with notable population changes on the largest two islands (Guardian Angel: 45 to 105 pairs [133% increase]; Tiburón: 164 to 109 pairs [34% decrease]). The minimum estimated Osprey population on the Sonora mainland decreased in a manner similar to adjacent Isla Tiburón, i.e., by 26%, from 214 pairs in 1993 to 158 pairs in 2006. In contrast, the population in coastal Sinaloa, which had increased by 150% between 1977 and 1993, grew again by 58% between 1993 and 2006, from 180 to 285 pairs. Our survey confirmed previously described patterns of rapid population changes at a local level, coupled with apparent shifts in spatial distribution. The large ground-nesting population that until recently nested on two islands in San Ignacio Lagoon ( Pacific Ocean side, Baja California) was no longer present on the islands in 2006, but an equivalent number of pairs were found to the north and south of the lagoon, nesting in small towns and along adjoining overhead electric lines, with no overall change in population size for that general area (198 pairs in 1992; 199 in 2006). Use of artificial nesting structures was 4.3% in 1977 and 6.2% in 1992/1993, but jumped to 26.4% in 2006. Use of poles that support overhead electric lines poses a risk of electrocution to Ospreys and also causes power outages and fires. We recommend modification of these poles to safely accommodate Osprey nests, as has been successfully accomplished in many countries.

Journal of Raptor Research↗

Assessment of thermal maturity trends in Devonian-Mississippian source rocks using Raman spectroscopy: Limitations of peak-fitting method

The thermal maturity of shale is often measured by vitrinite reflectance (VRo). VRo measurements for the Devonian–Mississippian black shale source rocks evaluated herein predicted thermal immaturity in areas where associated reservoir rocks are oil-producing. This limitation of the VRo method led to the current evaluation of Raman spectroscopy as a suitable alternative for developing correlations between thermal maturity and Raman spectra. In this study, Raman spectra of Devonian–Mississippian black shale source rocks were regressed against measured VRo or sample-depth. Attempts were made to develop quantitative correlations of thermal maturity. Using sample-depth as a proxy for thermal maturity is not without limitations as thermal maturity as a function of depth depends on thermal gradient, which can vary through time, subsidence rate, uplift, lack of uplift, and faulting. Correlations between Raman data and vitrinite reflectance or sample-depth were quantified by peak-fitting the spectra. Various peak-fitting procedures were evaluated to determine the effects of the number of peaks and maximum peak widths on correlations between spectral metrics and thermal maturity. Correlations between D-frequency, G-band full width at half maximum (FWHM), and band separation between the G- and D-peaks and thermal maturity provided some degree of linearity throughout most peak-fitting assessments; however, these correlations and those calculated from the G-frequency, D/G FWHM ratio, and D/G peak area ratio also revealed a strong dependence on peak-fitting processes. This dependency on spectral analysis techniques raises questions about the validity of peak-fitting, particularly given the amount of subjective analyst involvement necessary to reconstruct spectra. This research shows how user interpretation and extrapolation affected the comparability of different samples, the accuracy of generated trends, and therefore, the potential of the Raman spectral method to become an industry benchmark as a thermal maturity probe. A Raman method devoid of extensive operator interaction and data manipulation is quintessential for creating a standard method.

Frontiers in Energy Research↗

Long-term trends in regional wet mercury deposition and lacustrine mercury concentrations in four lakes in Voyageurs National Park

Although anthropogenic mercury (Hg) releases to the environment have been substantially lowered in the United States and Canada since 1990, concerns remain for contamination in fish from remote lakes and rivers where atmospheric deposition is the predominant source of mercury. How have aquatic ecosystems responded? We report on one of the longest known multimedia data sets for mercury in atmospheric deposition: aqueous total mercury (THg aq ), methylmercury (MeHg aq ), and sulfate from epilimnetic lake-water samples from four lakes in Voyageurs National Park (VNP) in northern Minnesota; and total mercury (THg) in aquatic biota from the same lakes from 2001–2018. Wet Hg deposition at two regional Mercury Deposition Network sites (Fernberg and Marcell, Minnesota) decreased by an average of 22 percent from 1998–2018; much of the decreases occurred prior to 2009, with relatively flat trends since 2009. In the four VNP lakes, epilimnetic MeHg aq concentrations declined by an average of 44 percent and THg aq by an average of 27 percent. For the three lakes with long-term biomonitoring, temporal patterns in biotic THg concentrations were similar to patterns in MeHg aq concentrations; however, biotic THg concentrations declined significantly in only one lake. Epilimnetic MeHg aq may be responding both to a decline in atmospheric Hg deposition as well as a decline in sulfate deposition, which is an important driver of mercury methylation in the environment. Results from this case study suggest that regional- to continental-scale decreases in both mercury and sulfate emissions have benefitted aquatic resources, even in the face of global increases in mercury emissions.

Minnesota↗