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National Acid Precipitation Assessment Program Report to Congress: An integrated assessment

Acid deposition, more commonly known as acid rain, occurs when emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) react in the atmosphere (with water, oxygen, and oxidants) to form various acidic compounds. These acidic compounds then fall to earth in either a wet form (rain, snow, and fog) or a dry form (gases, aerosols, and particles). Prevailing winds transport the acidic compounds hundreds of miles, often across state and national borders. At certain levels the acidic compounds, including small particles such as sulfates and nitrates can cause many negative human health and environmental effects. While ecosystems are subject to many stresses, including land-use changes, climate change, and variations in hydrologic and meteorologic cycles, the scientific literature has clearly demonstrated that these pollutants can: • Degrade air quality, • Impair visibility, • Damage public health, • Acidify lakes and streams, • Harm sensitive forests, • Harm sensitive coastal ecosystems, and • Accelerate the decay of building materials, paints, and cultural artifacts such as buildings, statues, and sculptures. Title IV was passed by Congress as part of the 1990 Clean Air Act Amendments to reduce emissions of SO 2 and NO x from fossil fuel-burning power plants in order to protect ecosystems suffering damage from acid deposition and to improve air quality. At the same time, the National Acid Precipitation Assessment Program (NAPAP) was asked to periodically assess and report to Congress on the implementation of the Acid Rain Program, recent scientific knowledge surrounding acid deposition and its effects, and the reduction in acid deposition necessary to prevent adverse ecological effects. This NAPAP Report focuses primarily on emission reductions from power plants, both in terms of assessing past reductions under the Acid Rain Program and in projecting the ecological effects of additional reductions of SO 2 and NO x . It should be noted that power generation currently contributes approximately 69% of the SO 2 emissions and 22% of the NO x emissions nationwide. This contribution is decreasing as emissions from power generation continue to decrease, making the other sources of these pollutants more prominent. Modeling suggests that even if SO 2 emissions from power generation were reduced to zero, some lakes and streams would remain acidic due to acid deposition. However, there are several other regulations that reduce emissions of SO 2 and NO x from these non-power generation sources, such as the Tier II mobile source standards, the Heavy Duty Diesel standards, and the Clean Air Non-Road Diesel Rule, that have also been promulgated since 1990. These regulations, primarily designed to bring counties into attainment with fine particle and ozone air quality standards, also incidentally reduce emissions that contribute to acid deposition. Implementation of Title IV has successfully and substantially reduced emissions of SO 2 and NO x from power generation at a significantly lower cost than expected: • In 2002, SO 2 emissions were 10.2 million tons, 35% lower than 1990 emissions and 40% lower than 1980 emissions.* • In 2002, NO x emissions were 4.5 million tons, 33% lower than 1990 emissions. In addition, SO 2 emissions from all sources have decreased by 32% since 1990 and emissions of NO x from all sources have decreased by 12% since 1990. Power generating sources continue to close in on the goal of reducing power plant SO 2 emissions from 1980 levels by 50% (to 8.95 million tons) as required by the 1990 Clean Air Act. Power generating sources have also exceed­ed the goal of a two million ton reduction in NO x emissions from projected 2000 levels as required by the 1990 Clean Air Act. These emission reductions have contributed to measurable improvements in air quality, reductions in acid deposition, and the beginnings of recovery of acid-sensitive waters in some areas: • SO2 concentrations in the atmosphere (a precursor to fine particles and acid deposition) have decreased since 1990. Average annual SO2 concentrations in the Northeast in 2000–2002 were 40% lower than they were in 1989–1991, concentrations in the mid-Atlantic were 30% lower, concentrations in the Southeast were 35% lower, and concentrations in the Midwest were 45% lower. • Sulfate concentrations in the atmosphere (a major component of fine particles, especially in the East) have decreased since 1990 as well. Average annual sulfate concentrations in the Northeast and Midwest in 2000–2002 were approximately 30% lower than they were in 1989–1991, and concentrations in the mid-Atlantic and Southeast were 25% lower. • Wet sulfate deposition, a major component of acid rain, has also decreased since 1990. Average annual sulfate deposition in the Northeast in 2000–2002 was 40% lower than it was in 1989–1991, deposition in the mid-Atlantic and Midwest was 35% lower, and deposition in the Southeast was 25% lower. • Wet nitrate deposition has not decreased regionally from historical levels because of the relatively moderate NO x reduction from power plants and the continuing large contribution (over 50% of total NOx emissions) from other sources of NO x such as vehicles and nonroad vehicles. • Although visibility has begun to improve in some parts of the U.S., there is still significant impairment of visibility in many national parks and other Class I areas throughout the U.S. • Acid neutralizing capacity is beginning to rise in some surface waters in the Northeast, including lakes in the Adirondack Mountains (see graphic below). This is an indication that recovery from acidification is occurring in those areas.

Report to Congress↗

Appendix E. Water quality and hydrology of Green Lake, Wisconsin, and the response in its near-surface water-quality and metalimnetic dissolved oxygen minima to changes in phosphorus loading

Green Lake is the deepest natural inland lake in Wisconsin, USA, with a maximum depth of about 72 meters (m). In the early 1900’s, the lake was believed to have very good water quality (low nutrient concentrations and good water clarity), with low dissolved oxygen (DO) concentrations only in the deepest part of the lake. Because of increased phosphorus (P) inputs from anthropogenic activities in its watershed, total phosphorus (TP) concentrations in the lake increased, which led to increased algal production and low DO concentrations not only occurring in its deepest areas but also in the middle of the water column (metalimnion). Routine monitoring of the lake and its tributaries has been conducted by the U.S. Geological Survey since 2004 and 1988, respectively. Results from this monitoring led to the Wisconsin Department of Natural Resources (WDNR) listing the lake as impaired because of low DO concentrations in the metalimnion, with elevated TP concentrations identified as the cause of impairment. As part of this study, comprehensive sampling of the lake and its tributaries was conducted in 2017–2018 to augment ongoing monitoring and further describe the low DO concentrations in the lake (especially in the metalimnion). Empirical and process-driven water quality models were then used to determine the causes of the low DO concentrations and the magnitude of P load reductions needed to improve the water quality of the lake to meet multiple water-quality goals, including the WDNR criteria for TP and DO. Data from previous studies showed that DO concentrations in the metalimnion decreased slightly as summer progressed in the early 1900’s, but since the late 1970s have typically dropped below 5 milligrams per liter (mg/L), which is the WDNR criterion for impairment. During 2014–2018 (baseline period for this study), the near-surface geometric-mean TP concentration during June–September in the east side of the lake was 0.020 mg/L and in the west side was 0.016 mg/L (both were below the 0.015 mg/L WDNR criterion for the lake), and the minimum metalimnetic DO concentrations measured in August ranged from 1.0 to 4.7 mg/L. It was believed that the degradation in water quality was caused by excessive P inputs to the lake; therefore, the total P inputs to the lake were estimated. The mean annual external P load during 2014–2018 was estimated to be 8,980 kilograms per year (kg/yr), of which monitored and unmonitored tributary inputs contributed 84 percent, atmospheric inputs contributed 8 percent, waterfowl contributed 7 percent, and septic systems contributed 1 percent. At fall turnover, internal sediment recycling contributed an additional 7,040 kg that increased TP concentrations in shallow areas of the lake by about 0.020 mg/L. The elevated TP concentrations then persisted until the following spring. On an annual basis, however, there is a net deposition of P to the bottom sediments. Empirical models were used to describe how the near-surface water quality of Green Lake would be expected to respond to changes in external P loading. Predictions from the models showed a relatively linear response between P loading and TP and chlorophyll-a (Chl-a) concentrations in the lake, with the changes in TP and Chl-a concentrations being less on a percentage basis (50–60 percent for TP and 30–70 percent for Chl-a) than the changes in P loading. Mean summer water clarity, indicated by Secchi disk depths, had a larger response to decreases in P loading than to increases in loading. Based on these relations, external P loading to the lake would need to be decreased from 8,980 kg/yr to about 5,460 kg/yr for the geometric mean June–September TP concentration on the east side of the lake, with higher TP concentrations than the west side, to reach the WDNR criterion of 0.015 mg/L. This reduction of 3,520 kg/yr equates to a 46-percent reduction in the potentially controllable external P sources (all external sources except precipitation, atmospheric deposition, and waterfowl) from that measured during water years (WYs) 2014–2018. The total external P loading would need to be decreased to 7,680 kg/yr (17-percent reduction in potentially controllable external P sources) for near-surface June–September TP concentrations in the west side of the lake to reach 0.015 mg/L. Total external P loading would need to be decreased to 3,870–5,320 kg/yr for the lake to be classified as oligotrophic, with a near-surface June-September TP concentration of 0.012 mg/L. Results from the hydrodynamic water-quality model GLM-AED (General Lake Model coupled to the Aquatic Ecodynamics modeling library) indicated that metalimnetic DO minima are driven by external P loading and internal sediment recycling that lead to high TP concentrations during spring and early summer, which in turn lead to high phytoplankton production, high metabolism and respiration, and ultimately DO consumption in the upper, warmer areas of the metalimnion. GLM-AED results indicated that settling of organic material during summer may be slowed by the colder, denser, and more viscous water in the metalimnion and increase DO consumption. Based on empirical evidence comparing minimum metalimnetic DO concentrations with various meteorological, hydrologic, water quality, and in-lake physical factors, lower metalimnetic DO concentrations occurred when there was warmer metalimnetic water temperatures, higher near-surface Chl-a and TP concentrations, and lower Secchi depths during summer. GLM-AED results indicated that the external P load would need to be reduced to about 4,010 kg/yr, a 57-percent reduction from that measured in 2014–2018, to eliminate the occurrence of metalimnetic DO minima of less than 5 mg/L in over 75 percent of the years (the target provided by the WDNR). Large reductions in external P loading are expected to have an immediate effect on the near-surface TP concentrations and metalimnetic DO concentrations in Green Lake. However, it may take several years for the full effects of the external load reduction to be observed because internal sediment recycling is an important source of P for the following spring.

Wisconsin↗

Estimating belowground carbon stocks in isolated wetlands of the Northern Everglades Watershed, central Florida, using ground penetrating radar (GPR) and aerial imagery

Peat soils store a large fraction of the global soil carbon (C) pool and comprise 95% of wetland C stocks. While isolated freshwater wetlands in temperate and tropical biomes account for more than 20% of the global peatland C stock, most studies of wetland soil C have occurred in expansive peatlands in northern boreal and subarctic biomes. Furthermore, the contribution of small depressional wetlands in comparison to larger wetland systems in these environments is very uncertain. Given the fact that these wetlands are numerous and variable in terms of their internal geometry, innovative methods are needed for properly estimating belowground C stocks and their overall C contribution to the landscape. In this study, we use a combination of ground penetrating radar (GPR), aerial imagery, and direct measurements (coring) in conjunction with C core analysis to develop a relation between C stock and surface area, and estimate the contribution of subtropical depressional wetlands to the total C stock of pine flatwoods at the Disney Wilderness Preserve (DWP), Florida. Additionally, GPR surveys were able to image collapse structures underneath the peat basin of depressional wetlands, depicting lithological controls on the formation of depressional wetlands at the DWP. Results indicate the importance of depressional wetlands as critical contributors to the landscape C budget at the DWP and the potential of GPR-based approaches for (1) rapidly and noninvasively estimating the contribution of depressional wetlands to regional C stocks and (2) evaluating the formational processes of depressional wetlands.

Florida↗

Insights into plant water uptake from xylem-water isotope measurements in two tropical catchments with contrasting moisture conditions

Water transpired by trees has long been assumed to be sourced from the same subsurface water stocks that contribute to groundwater recharge and streamflow. However, recent investigations using dual water stable isotopes have shown an apparent ecohydrological separation between tree-transpired water and stream water. Here we present evidence for such ecohydrological separation in two tropical environments in Puerto Rico where precipitation seasonality is relatively low and where precipitation is positively correlated with primary productivity. We determined the stable isotope signature of xylem water of 30 mahogany ( Swietenia spp.) trees sampled during two periods with contrasting moisture status. Our results suggest that the separation between transpiration water and groundwater recharge/streamflow water might be related less to the temporal phasing of hydrologic inputs and primary productivity, and more to the fundamental processes that drive evaporative isotopic enrichment of residual soil water within the soil matrix. The lack of an evaporative signature of both groundwater and streams in the study area suggests that these water balance components have a water source that is transported quickly to deeper subsurface storage compared to waters that trees use. A Bayesian mixing model used to partition source water proportions of xylem water showed that groundwater contribution was greater for valley-bottom, riparian trees than for ridge-top trees. Groundwater contribution was also greater at the xeric site than at the mesic–hydric site. These model results (1) underline the utility of a simple linear mixing model, implemented in a Bayesian inference framework, in quantifying source water contributions at sites with contrasting physiographic characteristics, and (2) highlight the informed judgement that should be made in interpreting mixing model results, of import particularly in surveying groundwater use patterns by vegetation from regional to global scales.

Hydrological Processes↗

Influence of mineral weathering reactions on the chemical composition of soil water, springs, and ground water, Catoctin Mountains, Maryland

During 1983 and 1984, wet precipitation was primarily a solution of dilute sulphuric acid, whereas calcium and bicarbonate were the major ions in springs and ground water in two small watersheds with a deciduous forest cover in central Maryland. Dominant ions in soil water were calcium, magnesium, and sulphate. The relative importance of mineral weathering reactions on the chemical composition of these subsurface waters was compared to the contribution from wet precipitation, biological processes, and road deicing salts. Mineral reaction models, developed from geochemical mass-balance relationships, involved reactions of primary and secondary minerals in metabasalt and metarhyolite with hydrogen ion. Geochemical weathering reactions account for the majority of total ion equivalents in soil water (46 per cent), springs (51 per cent), and ground water (68 to 77 per cent). The net contribution of total ion equivalents from biological processes was 20 and 16 per cent for soil water and springs, respectively, but less than 10 per cent for ground water. The contribution of total ion equivalents from deicing salts (10 to 20 per cent) was related to proximity to roads. Strong acids in precipitation contributed 44 per cent of the total amount of hydrogen ions involved in mineral-weathering reactions for ground water in contact with metarhyolite compared to 25 per cent for ground water in contact with metabasalt, a less resistant rock type to weathering.

Hydrological Processes↗

Carbon budget for a subtropical seagrass dominated coastal lagoon: How important are seagrasses to total ecosystem net primary production?

It has been assumed that because seagrasses dominate macrophyte biomass in many estuaries they also dominate primary production. We tested this assumption by developing three carbon budgets to examine the contribution of autotrophic components to the total ecosystem net primary production (TENPP) of Lower Laguna Madre, Texas. The first budget coupled average photosynthetic parameters with average daily irradiance to calculate daily production. The second budget used average photosynthetic parameters and hourly in situ irradiance to estimate productivity. The third budget integrated temperature-adjusted photosynthetic parameters (using Q 10 =2) and hourly in situ irradiance to estimate productivity. For each budget TENPP was calculated by integrating production from each autotroph based on the producers’ areal distribution within the entire Lower Laguna Madre. All budgets indicated that macroalgae account for 33–42% of TENPP and seagrasses consistently accounted for about 33–38%. The contribution by phytoplankton was consistently about 15–20%, and the contribution from the benthic microalgae varied between 8% and 36% of TENPP, although this may have been underestimated due to our exclusion of the within bed microphytobenthos component. The water column over the seagrass beds was net heterotrophic and consequently was a carbon sink consuming between 5% and 22% of TENPP, TENPP ranged between 5.41×10 10 and 2.53×10 11 g C yr −1 , depending on which budget was used. The simplest, most idealized budget predicted the highest TENPP, while the more realistic budgets predicted lower values. Annual production rates estimated using the third budget for Halodule urightii and Thalassia testudinum compare well with field data. Macroalgae and microalgae contribute 50–60% of TENPP, and seagrass may be more important as three-dimensional habitat (i.e., structure) than as a source of organic carbon to the water column in Lower Laguna Madre.

Texas↗

Carbon sources in the sediments of a restoring vs. historically unaltered salt marsh

Salt marshes provide the important ecosystem service of carbon storage in their sediments; however, little is known about the sources of such carbon and whether they differ between historically unaltered and restoring systems. In this study, stable isotope analysis was used to quantify carbon sources in a restoring, sparsely vegetated marsh (Restoring) and an adjacent, historically unaltered marsh (Reference) in the Nisqually River Delta (NRD) of Washington, USA. Three sediment cores were collected at “Inland” and “Seaward” locations at both marshes ~ 6 years after restoration. Benthic diatoms, C3 plants, C4 plants, and particulate organic matter (POM) were collected throughout the NRD. δ 13 C and δ 15 N values of sources and sediments were used in a Bayesian stable isotope mixing model to determine the contribution of each carbon source to the sediments of both marshes. Autochthonous marsh C3 plants contributed 73 ± 10% (98 g C m −2 year −1 ) and 89 ± 11% (119 g C m −2 year −1 ) to Reference-Inland and Reference-Seaward sediment carbon sinks, respectively. In contrast, the sediment carbon sink at the Restoring Marsh received a broad assortment of predominantly allochthonous materials, which varied in relative contribution based on source distance and abundance. Marsh POM contributed the most to Restoring-Seaward (42 ± 34%) (69 g C m −2 year −1 ) followed by Riverine POM at Restoring-Inland (32 ± 41%) (52 g C m −2 year −1 ). Overall, this study demonstrates that largely unvegetated, restoring marshes can accumulate carbon by relying predominantly on allochthonous material, which comes mainly from the most abundant and closest estuarine sources. ces.

Washington↗

Relative importance of macroalgae and phytoplankton to nearshore consumers and growth across climatic conditions in the northern Gulf of Alaska

Macroalgae and phytoplankton support the base of highly productive nearshore ecosystems in cold-temperate regions. To better understand their relative importance to nearshore food webs, this study considered four regions in the northern Gulf of Alaska where three indicator consumers were collected, filter-feeding mussels ( Mytilus trossulus ), pelagic-feeding Black Rockfish ( Sebastes melanops ), and benthic-feeding Kelp Greenling ( Hexagrammos decagrammus ). The study objectives were to (1) estimate the proportional contributions of macroalgal and phytoplankton organic matter using carbon and nitrogen stable isotopes, (2) determine if macroalgal use affected consumer growth using annual growth rings in shells or otoliths, and (3) describe changes in organic matter use and growth during the Pacific Marine Heatwave (PMH; 2014–2016) in one consumer, mussels. Macroalgae were the major organic matter source (> 60%) to the diet for all three consumers. The relationships between macroalgal contribution and growth were neutral for both fish species and significantly positive for mussels. During the PMH, mussels had a drop (> 10%) in macroalgal contributions and grew 45% less than in other time periods. Simultaneously, the relationship between macroalgal contribution and mussel growth was strongest during the PMH, explaining 48% variation compared to 3–12% before or after the PMH. Collectively, the results suggest that macroalgae is likely more important to cold-temperate nearshore food webs than phytoplankton. Management actions aimed at conserving and expanding macroalgae are likely to benefit nearshore food webs under all climate scenarios and especially during marine heatwaves.

Alaska↗

Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.-1: Buffering capacity of dissolved organic carbon in soil solutions

Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai − , derived from DOC at sample pH and the concentration of organic anion, Ax − at the equivalence point were calculated using car☐yl contents from isolated and purified humic material from soil solutions. Subtracting Ax − from Ai − yields the contribution of humic substances to the buffering capacity (A equiv. − ). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado.

Colorado↗

A radiogenic isotope tracer study of transatlantic dust transport from Africa to the Caribbean

Many studies have suggested that long-range transport of African desert dusts across the Atlantic Ocean occurs, delivering key nutrients and contributing to fertilization of the Amazon rainforest. Here we utilize radiogenic isotope tracers – Sr, Nd and Pb – to derive the provenance, local or remote, and pathways of dust transport from Africa to the Caribbean. Atmospheric total suspended particulate (TSP) matter was collected in 2008 on quartz fibre filters, from both sides of the Atlantic Ocean at three different locations: in Mali (12.6°N, 8.0°W; 555 m a.s.l.), Tobago (11.3°N, 60.5°W; 329 m a.s.l.) and the U.S. Virgin Islands (17.7°N, 64.6°W; 27 m a.s.l.). Both the labile phase, representative of the anthropogenic signal, and the refractory detrital silicate fraction were analysed. Dust deposits and soils from around the sampling sites were measured as well to assess the potential contribution from local sources to the mineral dust collected. The contribution from anthropogenic sources of Pb was predominant in the labile, leachate phase. The overall similarity in Pb isotope signatures found in the leachates is attributed to a common African source of anthropogenic Pb, with minor inputs from other sources, such as from Central and South America. The Pb, Sr and Nd isotopic compositions in the silicate fraction were found to be systematically more radiogenic than those in the corresponding labile phases. In contrast, Nd and Sr isotopic compositions from Mali, Tobago, and the Virgin Islands are virtually identical in both leachates and residues. Comparison with existing literature data on Saharan and Sahelian sources constrains the origin of summer dust transported to the Caribbean to mainly originate from the Sahel region, with some contribution from northern Saharan sources. The source regions derived from the isotope data are consistent with 7-day back-trajectory analyses, demonstrating the usefulness of radiogenic isotopes in tracing dust provenance and atmospheric transport.

Africa;Atlantic Ocean;Caribbean;Sahara;Sahel↗

Mitigating climate change by abating coal mine methane: A critical review of status and opportunities

Methane has a short atmospheric lifetime compared to carbon dioxide (CO 2 ), ∼decade versus ∼centuries, but it has a much higher global warming potential (GWP), highlighting how reducing methane emissions can slow the rate of climate change. When considering the contribution of greenhouse gas (GHG) emissions to current global warming (2010–2019) relative to the industrial revolution (1850–1900) levels, methane contributes 0.5 °C or ∼ a third of the total. The most recent post-2023 global estimates of methane emissions by bottom-up (BU) and top-down (TD) approaches for the coal mining sector are in the range of ∼41 ± 3 Tg yr −1 and 33 ± 5 Tg yr −1 , respectively. This divergence, notwithstanding overlapping confidence intervals, is a result of differences between applied TD global inversion models and BU emission inventories. Further research can help to better refine emissions from the various contributing coal mine methane (CMM) emissions sources. The coal mining sector accounts for over 10 % of global anthropogenic methane emissions. The contribution of CMM emissions to the global budget have increased since 2000, although upward and downward regional trends have been observed.

International Journal of Coal Geology↗

Assigning land use to supply wells for the statistical characterization of regional groundwater quality: Correlating urban land use and VOC occurrence

Many national and regional groundwater studies have correlated land use "near" a well, often using a 500 m radius circle, with water quality. However, the use of a 500 m circle may seem counterintuitive given that contributing areas are expected to extend up-gradient from wells, and not be circular in shape. The objective of this study was to evaluate if a 500 m circle is adequate for assigning land use to a well for the statistical correlation between urban land use and the occurrence of volatile organic compounds (VOCs). Land use and VOC data came from 277 supply wells in four study areas in California. Land use was computed using ten different-sized circles and wedges (250 m to 10 km in radius), and three different-sized "searchlights" (1-2 km in length). We define these shapes as contributing area surrogates (CASs), recognizing that a simple shape is at best a surrogate for the actual contributing area. The presence or absence of correlation between land use and the occurrence of VOCs was evaluated using Kendall's tau (??). Values of ?? were within 10% of one another for wedges and circles ranging in size from 500 m to 2 km, with correlations remaining statistically significant (p < 0.05) for all CAS sizes and shapes, suggesting that a 500 m circular CAS is adequate for assigning land use to a well. Additional evaluation indicated that urban land use is autocorrelated at distances ranging from 8 to 36 km. Thus, urban land use in a 500 m CAS is likely to be predictive of urban land use in the actual contributing area.

Journal of Hydrology↗

Petrologic constraints on the thermal structure of the Cascades arc

Primitive late Cenozoic basaltic lavas from the Cascades volcanic arc near latitude 46°N comprise two distinct compositional groups. Group I includes samples with low Ba/Nb (<20) and other compositional similarities to oceanic island and MORB lavas from within-plate settings. In contrast, Group II exhibits enrichment of Ba and large-ion lithophile elements (LILE) and depletion of Nb and high-field strength elements (HFSE) as seen commonly in calcalkalic lavas from other volcanic arcs. Lavas of both groups are widely distributed across the transect, and Group I lavas are found as much as 30–40 km trenchward of stratovolcanoes that define the High Cascades ‘volcanic front (VF)’. The most primitive lavas are sparsely porphyritic, have elevated Ni, Cr, and Mg#, high calculated magmatic temperatures (1200–1300 °C), and lack evidence of shallow (crustal level) storage and crystallization. Compositions of parental liquids were calculated for each primitive sample on the premise of Fe–Mg equilibrium with mantle peridotite. Assuming that such magmas ascended rapidly from accumulation zones in the mantle, we estimate P and T of segregation. We infer that (a) Group I magmas ascended from systematically greater depths (∼50–70 km) than Group II (∼30–50 km), implying the possible existence of compositional stratification in the mantle wedge; (b) Group I basalts show the least evidence for slab-derived contributions in their sources despite their apparently greater segregation depths (approaching the locus of the Cascadia slab beneath the frontal arc region); (c) Group II lavas with the strongest slab compositional signature have temperatures far exceeding the wet peridotite solidus at high pressure; and (d) the inferred thermal structure of the mantle wedge is very warm, implying a significant component of mantle upwelling and convection. Group I lavas are interpreted as decompression melts from this mantle, and their compositions suggest that their source was little modified by slab-derived contributions. We speculate that melting to produce Group II magmas occurs in the shallow mantle, possibly in response to heating by hot ascending Group I magmas. If true, it seems unlikely that the slab-like signal in Group II lavas can be attributed to modern slab inputs; rather, we postulate that this signature may reflect melting of lithospheric mantle domains containing a ‘stored’ slab-derived component inherited from earlier stages of Cascadia subduction. This scenario differs from the standard paradigm for subduction zones (SZs), and stresses the importance of convecting asthenospheric mantle in driving arc magmatism, particularly in warm subduction zones where slab fluid contributions likely are minimal. In contrast, because tectonic conditions in more typical volcanic arcs favor subduction of cooler, less dehydrated oceanic lithosphere, slab-derived fluids may promote extensive flux-melting in the wedge. Such melts may dominate the magmatic output and mask wedge contributions. The Cascade arc thus provides rarely afforded insights into arc magma genesis.

British Columbia, California, Oregon, Washington↗

Gas emissions from the Sulphur Bank Mercury Mine hydrothermal system, Clear Lake volcanic field, California

The Sulphur Bank Mercury Mine (SBMM) hydrothermal system offers insights into active degassing processes in the Clear Lake volcanic field (CLVF), a high-threat region based on its record of Holocene eruptions and proximity to populated areas. Here we present chemical and isotopic analyses of gas samples collected between 2015 and 2023, along with the first comprehensive CO 2 flux survey of the SBMM area conducted in 2023. Sampled gases are CO 2 - and CH 4 -rich (≥84 and 6 mol% in dry gas, respectively) with high mantle-derived helium contributions ( 3 He/ 4 He = 6.54–7.86 R C /R A ). Carbon isotopic compositions of CO 2 (δ 13 C = −10.0 to −9.5 ‰) and CH 4 (δ 13 C = −35.8 ‰) indicate mixed sources, with significant contributions from metamorphism of organic-rich Franciscan Complex rocks hosting the hydrothermal system. Modeling of gas compositions shows that scrubbing by interaction with air-saturated groundwater strongly influences observed compositional variability. From our CO₂ flux measurements, we estimate the deeply derived CO 2 emission rate from the SBMM hydrothermal area (0.2 km 2 ) at 240 t d −1 , comparable to many quiescently degassing volcanoes worldwide. We also provide a first-order estimate of CH 4 emissions at approximately 0.5 t d −1 . Our findings establish crucial baseline data for future volcanic monitoring efforts, enhancing detection capabilities for potential changes in this active hydrothermal system. This work contributes to the broader understanding of volatile contributions from volcanic and metamorphic sources to the global carbon budget, while highlighting the strong influence of bedrock geology on gas compositions in the CLVF.

California↗

Incorporating interpreter variability into estimation of the total variance of land cover area estimates under simple random sampling

Area estimates of land cover and land cover change are often based on reference class labels determined by analysts interpreting satellite imagery and aerial photography. Different interpreters may assign different reference class labels to the same sample unit. This interpreter variability is typically not accounted for in variance estimators applied to area estimates of land cover. A simple measurement model provides the basis for an estimator of the total variance ( V Total ) that takes into account both sampling variance and interpreter variance. This method requires two or more reference class interpretations (i.e., repeated measurements) obtained by analysts, working independently of each other, for the full sample or a random subsample of the full sample. Estimators of the total variance ( V &#x302; Total "> V̂Total ) and the variance component attributable to interpreters ( V &#x302; 1 "> V̂1 ) were obtained for the case of two reference class interpretations per repeated sample unit. To evaluate the effect of interpreter variability on variance estimation, we used land cover reference data interpreted by seven analysts who each interpreted the same 300 sample pixels from a region of the Pacific Northwest of the United States. From these data, we estimated the contribution of interpreter variance to the total variance (i.e., V &#x302; 1 / V &#x302; Total "> V̂1/V̂Total ) and the relative bias of the standard simple random sampling variance estimator ( V &#x302; stand "> V̂stand ) as an estimator of V Total , defined as 100%*( V &#x302; stand &#x2212; V &#x302; Total "> V̂stand−V̂Total )/ V &#x302; Total "> V̂Total . For each of five land cover classes, we computed V &#x302; 1 "> V̂1 , V &#x302; Total "> V̂Total , and V &#x302; stand "> V̂stand using the sample data from each of the 21 possible pairwise combinations of the seven interpreters, and then calculated the mean of V &#x302; 1 / V &#x302; Total "> V̂1/V̂Total and the mean of the estimated relative bias of V &#x302; stand "> V̂stand over these 21 pairs. Based on the mean of V &#x302; 1 / V &#x302; Total "> V̂1/V̂Total per class, interpreter variance contributed from 25% (cropland) to 76% (grass/shrub) of the total variance, indicating that interpreter variance was a non-negligible component of the total variance. Typically, the standard variance estimator, V &#x302; stand "> V̂stand , underestimated the total variance with the mean estimated relative bias ranging from −3% (cropland) to −33% (grass/shrub). Classes with greater inconsistency between pairs of interpreters had larger contributions of interpreter variance to the total variance ( V &#x302; 1 / V &#x302; Total "> V̂1/V̂Total ) and larger negative estimated relative bias of V &#x302; stand "> V̂stand . Given that interpreter variance can contribute substantially to the total variance, the repeated measurements approach offers a practical way to incorporate this variability into an estimator of the total variance.

Washington↗

Processes controlling the episodic streamwater transport of atrazine and other agrichemicals in an agricultural watershed

Episodic streamwater transport of atrazine (a common agricultural herbicide) and nutrients has been observed throughout agricultural watersheds in the United States and poses a serious threat to the quality of its water resources. Catchment-scale atrazine and nutrient transport processes after agricultural application are still poorly understood, and predicting episodic streamwater composition remains an elusive goal. We instrumented a 1.2-km 2 agricultural catchment near Harrisonburg, Virginia, and examined streamwater, overland flow, soil water, groundwater, and rainfall during the summer of 1998. Storm chemographs demonstrated different patterns for constituents derived primarily from weathering (silica and calcium), compared to constituents derived primarily from early spring land applications (nitrate, atrazine, DOC, potassium, chloride, and sulfate). During storms, the concentrations of silica and calcium decreased, the atrazine response was variable, and the concentrations of nitrate, DOC, potassium, chloride, and sulfate increased; the elevated nitrate signal lagged several hours behind the other elevated constituents. Graphical and statistical analyses indicated a relatively stable spring-fed baseflow was modified by a mixture of overland flow and soil water. A rapid, short-duration overland-flow pulse dominated the streamflow early in the event and contributed most of the potassium, DOC, chloride, suspended sediment, and atrazine. A longer-duration soil–water pulse dominated the streamflow later in the event and contributed the nitrate as well as additional potassium, DOC, sulfate, and atrazine. The contributions to the episodic streamflow were quantified using a flushing model in which overland-flow and soil–water concentrations decreased exponentially with time during an episode. Flushing time constants for the overland-flow and soil–water reservoirs were calculated on a storm-by-storm basis using separate tracers for each time-variable reservoir. Initial component concentrations were estimated through regression analyses. Mass-balance calculations were used for flow separations and to predict the observed streamwater composition. Model forecasts indicated that reduced fertilizer and pesticide application (rather than elimination of overland-flow or soil–water contributions) was necessary to improve the episodic streamwater composition. This study provides important additional understanding of the catchment-scale processes by which land-applied pesticides and nutrients can move through agricultural systems.

Virginia↗

How do hydrological variability and human activities control the spatiotemporal changes of riverine nitrogen export in the Upper Mississippi River Basin?

Excessive nitrogen export from agricultural watersheds remains a critical water quality challenge, with the Upper Mississippi River Basin (UMRB) significantly contributing to downstream eutrophication and hypoxia in the Gulf. This study investigates the spatiotemporal dynamics of riverine nitrate plus nitrite (NO 3 – + NO 2 – -N) export across the UMRB at high spatial resolution (12-digit Hydrologic Unit Codes or HUC12 subwatershed scale) during 2001–2020 and quantifies the effects of anthropogenic activities and hydrological variability on riverine NO 3 – + NO 2 – -N export changes in the region between 2001–2005 and 2016–2020. Our results revealed hotspots of substantial increases in NO 3 – + NO 2 – -N yields across the UMRB, with distinct regional patterns in driving factors. Over the entire UMRB, NO 3 – + NO 2 – -N yields increased by 9.7 kg/ha/yr on average from 2001–2005 to 2016–2020, with anthropogenic activities contributing 4.8 kg/ha/yr and hydrological variability contributing 4.9 kg/ha/yr. The northern and western UMRB had combined influences from both anthropogenic activities and hydrological variability, while the east-central regions had predominantly hydrologically driven changes. Agricultural sources, including fertilizer, manure, and biological nitrogen fixation, collectively contributed over 80% of NO 3 – + NO 2 – -N loading throughout the basin. This framework for disentangling human and hydrological impacts provides critical insights for developing effective and targeted watershed management strategies to reduce nutrient losses and improve water quality.

Upper Mississippi River Basin↗

Simulated response of water quality in public supply wells to land use change

Understanding how changes in land use affect water quality of public supply wells (PSW) is important because of the strong influence of land use on water quality, the rapid pace at which changes in land use are occurring in some parts of the world, and the large contribution of groundwater to the global water supply. In this study, groundwater flow models incorporating particle tracking and reaction were used to analyze the response of water quality in PSW to land use change in four communities: Modesto, California (Central Valley aquifer); York, Nebraska (High Plains aquifer); Woodbury, Connecticut (Glacial aquifer); and Tampa, Florida (Floridan aquifer). The water quality response to measured and hypothetical land use change was dependent on age distributions of water captured by the wells and on the temporal and spatial variability of land use in the area contributing recharge to the wells. Age distributions of water captured by the PSW spanned about 20 years at Woodbury and >1,000 years at Modesto and York, and the amount of water <50 years old captured by the PSW ranged from 30% at York to 100% at Woodbury. Short‐circuit pathways in some PSW contributing areas, such as long irrigation well screens that crossed multiple geologic layers (York) and karst conduits (Tampa), affected age distributions by allowing relatively rapid movement of young water to those well screens. The spatial component of land use change was important because the complex distribution of particle travel times within the contributing areas strongly influenced contaminant arrival times and degradation reaction progress. Results from this study show that timescales for change in the quality of water from PSW could be on the order of years to centuries for land use changes that occur over days to decades, which could have implications for source water protection strategies that rely on land use change to achieve water quality objectives.

Water Resources Research↗