Prevailing impacts of river management on microplastic transport in contrasting US streams: Rethinking global microplastic flux estimations.

While microplastic inputs into rivers are assumed to be correlated with anthropogenic activities and to accumulate towards the sea, the impacts of water management on downstream microplastic transport are largely unexplored. A comparative study of microplastic abundance in Boulder Creek (BC), and its less urbanized tributary South Boulder Creek (SBC), (Colorado USA), characterized the downstream evolution of microplastics in surface water and sediments, evaluating the effects of urbanization and flow diversions on the up-to-downstream profiles of microplastic concentrations and loads. Water and sediment samples were collected from 21 locations along both rivers and microplastic properties determined by fluorescence microscopy and Raman spectroscopy. The degree of catchment urbanization affected microplastic patterns, as evidenced by greater water and sediment concentrations and loads in BC than the less densely populated SBC, which is consistent with the differences in the degree of urbanization between both catchments. Microplastic removal through flow diversions was quantified, showing that water diversions removed over 500 microplastic particles per second from the river, and caused stepwise reductions of downstream loads at diversion points. This redistribution of microplastics back into the catchment should be considered in large scale models quantifying plastic fate and transport to the oceans.

Nitrogen isotopes indicate vehicle emissions and biomass burning dominate ambient ammonia across Colorado's Front Range urban corridor.

Urban ammonia (NH3) emissions contribute to poor local air quality and can be transported to rural landscapes, impacting sensitive ecosystems. The Colorado Front Range urban corridor encompasses the Denver Metropolitan Area, rural farmland/rangeland and montane forest between the city and the Rocky Mountains. Reactive nitrogen emissions from the corridor are partly responsible for increased N deposition to the wildland-urban interface (WUI) in this region. To determine the significance of individual NH3 sources to WUI ecosystems, we measured the concentration and isotopic composition (δ15N-NH3) of ambient NH3(g) from April to October 2018 across a five-site urban to rural gradient in the corridor. The urban sites had higher NH3 concentrations and δ15N-NH3 values than the rural/suburban sites. Based on isotope mixing models, NH3 emission source contributions for all sites were fertilizer (12 ± 5.7%), livestock waste (18 ± 12%), vehicles (37 ± 23%), and biomass burning (34 ± 20%). Vehicle contributions were consistent across all months with an average of 35% and summer months showed a peak in biomass burning contributions (40%). As wildfires are projected to increase due to climate change, we stress a need for constraints on the isotopic signature of NH3 emitted from wildfires. Vehicle emissions contributed the greatest amount of NH3 (40%) at the urban sites while rural/suburban sites had higher agricultural contributions (41%). Had 2018 not had an anomalously high wildfire season, 46% and 60% of the NH3 would have been attributed to vehicle emissions at the WUI site and urban sites, respectively. NH3 emissions have historically been ascribed to agricultural activities but these findings illustrate the universal significance of vehicle emissions and the potential for sustained wildfire activity to be a primary contributor to NH3. Air quality (e.g., particulate matter) and nitrogen deposition reduction plans may benefit by including management practices that address vehicle NH3 emissions.

Wildfires: Identification of a new suite of aromatic polycarboxylic acids in ash and surface water.

Ash and surface water samples collected after wildfires in four different geographical locations (California, Colorado, Kansas and Alberta) were analyzed. The ash samples were leached with deionized water, and leachates were concentrated by solid phase extraction and analyzed by liquid chromatography/time-of-flight mass spectrometry. In addition, three surface water samples and a lysimeter water sample were collected from watersheds recently affected by fire in California and Colorado, and analyzed in similar fashion. A suite of benzene polycarboxylic acids (BPCAs), with two and three carboxyl groups and their corresponding isomers were identified for the first time in both ash leachates and water samples. Also found was a pyridine carboxylic acid (PCA), 3,5-pyridine dicarboxylic acid. Furthermore, putative identifications were made for other carboxylated aromatic acids: quinolinic, naphthalenic, and benzofuranoic acid carboxylates. The wildfire ashes, a controlled wood ash, and post-fire surface water samples suggest that burned woody material, along with surface plant-material and heated o-horizon soil organic matter, contribute to both BPCAs and PCAs in runoff. This study is the first of its kind to identify this suite of aromatic acids in wildfire ash and surface water samples. These data make an important contribution to the nature of dissolved organic matter from wildfire and are useful to better understand the impact of wildfire on water quality and drinking water sources.

Fates and fingerprints of sulfur and carbon following wildfire in economically important croplands of California, U.S.

Sulfur (S) is widely used in agriculture, yet little is known about its fates within upland watersheds, particularly in combination with disturbances like wildfire. Our study examined the effects of land use and wildfire on the biogeochemical "fingerprints," or the quantity and chemical composition, of S and carbon (C). We conducted our research within the Napa River Watershed, California, U.S., where high S applications to vineyards are common, and ~ 20% of the watershed burned in October 2017, introducing a disturbance now common across the warmer, drier Western U.S. We used a laboratory rainfall experiment to compare unburned and low severity burned vineyard and grassland soils. We then sampled streams draining sub-catchments with differing land use and degrees of burn and burn severity to understand combined effects at broader spatial scales. Before the laboratory experiment, vineyard soils had 2-3.5 times more S than grassland soils, while burned soils-regardless of land use-had 1.5-2 times more C than unburned soils. During the laboratory experiment, vineyard soil leachates had 16-20 times more S than grassland leachates, whereas leachate C was more variable across land use and burn soil types. Unburned and burned vineyard soils leached S with δ34S values enriched 6-15‰ relative to grassland soils, likely due to microbial S processes within vineyard soils. Streams draining vineyards also had the fingerprint of agricultural S, with ~2-5 fold higher S concentrations and ~ 10‰ enriched δ34S-SO42- values relative to streams draining non-agricultural areas. However, streams draining a higher fraction of burned non-agricultural areas also had enriched δ34S values relative to unburned non-agricultural areas, which we attribute to loss of 32S during combustion. Our findings illustrate the interacting effects of wildfire and land use on watershed S and C cycling-a new consideration under a changing climate, with significant implications for ecosystem function and human health.

Wildfire-driven changes in hydrology mobilize arsenic and metals from legacy mine waste.

Wildfires burning in watersheds that have been mined and since revegetated pose unique risks to downstream water supplies. A wildfire near Boulder, Colorado, that burned a forested watershed recovering from mining disturbance that occurred 80-160 years ago allowed us to 1) assess arsenic and metal contamination in streams draining the burned area for a five-year period after the wildfire and 2) determine the fire-affected hydrologic drivers that convey arsenic and metals to surface water. Most metal concentrations were low in the circumneutral waters draining the burned area. Water and sediment collected from streams downstream of the burned area had elevated arsenic concentrations during and after post-fire storms. Mining-related deposits were the main source of arsenic to streams. An increased proportion of overland flow relative to infiltration after the fire mobilized arsenic- and metal-rich surface deposits, along with wildfire ash and soil, into streams within and downstream of the burned area. The deposition of this material into stream channels resulted in the remobilization of arsenic for the five-year post-fire study period. It is also possible that enhanced subsurface flow after the fire increased contact of water with arsenic-bearing minerals exposed in underground mine workings. Other studies have reported that wildfire ash can be an important source of arsenic and metals to surface waters, but wildfire ash was not a major source of arsenic in this study. Predicted increases in frequency, size, and intensity of wildfires in the western U.S., a region with widely dispersed historical mines, suggest that the intersection of legacy mining and post-wildfire hydrologic response poses an increasing risk for water supplies.

Inorganic nitrogen wet deposition gradients in the Denver-Boulder metropolitan area and Colorado Front Range - Preliminary implications for Rocky Mountain National Park and interpolated deposition maps.

For the first time in the 40-year history of the National Atmospheric Deposition Program/National Trends Network (NADP/NTN), a unique urban-to-rural transect of wet deposition monitoring stations was operated as part of the NTN in 2017 to quantify reactive inorganic nitrogen wet deposition for adjacent urban and rural, montane regions. The transect of NADP stations (sites) was used to collect continuous precipitation depth and weekly wet-deposition samples in the Denver - Boulder, Colorado, urban corridor. Gradients in reactive inorganic nitrogen (Nr) concentrations and wet deposition were identified along the transect, which included Rocky Mountain National Park. Back trajectory modeling and stable isotopes suggested contribution of agricultural ammonia (NH3) to urban Nr wet deposition in Denver, but apportionment of wet-deposited Nr to agricultural versus urban mobile sources was not possible for this study. The results demonstrate the importance of multiple monitoring sites across an urban area in defining fine-scale geographic patterns in atmospheric deposition and its sources. Data from new sites located within 50 km of the urban area demonstrate that the urban influence does not extend as far as the inverse distance weighting would have suggested without such empirical monitoring data. It is important to determine the radius of influence of urban emissions and associated deposition on the interpolated deposition raster, which is constrained by a paucity of monitoring sites east of Denver.

Reassessing rainfall in the Luquillo Mountains, Puerto Rico: Local and global ecohydrological implications.

Mountains receive a greater proportion of precipitation than other environments, and thus make a disproportionate contribution to the world's water supply. The Luquillo Mountains receive the highest rainfall on the island of Puerto Rico and serve as a critical source of water to surrounding communities. The area's role as a long-term research site has generated numerous hydrological, ecological, and geological investigations that have been included in regional and global overviews that compare tropical forests to other ecosystems. Most of the forest- and watershed-wide estimates of precipitation (and evapotranspiration, as inferred by a water balance) have assumed that precipitation increases consistently with elevation. However, in this new analysis of all known current and historical rain gages in the region, we find that similar to other mountainous islands in the trade wind latitudes, leeward (western) watersheds in the Luquillo Mountains receive lower mean annual precipitation than windward (eastern) watersheds. Previous studies in the Luquillo Mountains have therefore overestimated precipitation in leeward watersheds by up to 40%. The Icacos watershed, however, despite being located at elevations 200-400 m below the tallest peaks and to the lee of the first major orographic barrier, receives some of the highest precipitation. Such lee-side enhancement has been observed in other island mountains of similar height and width, and may be caused by several mechanisms. Thus, the long-reported discrepancy of unrealistically low rates of evapotranspiration in the Icacos watershed is likely caused by previous underestimation of precipitation, perhaps by as much as 20%. Rainfall/runoff ratios in several previous studies suggested either runoff excess or runoff deficiency in Luquillo watersheds, but this analysis suggests that in fact they are similar to other tropical watersheds. Because the Luquillo Mountains often serve as a wet tropical archetype in global assessments of basic ecohydrological processes, these revised estimates are relevant to regional and global assessments of runoff efficiency, hydrologic effects of reforestation, geomorphic processes, and climate change.

Evaluation of wastewater contaminant transport in surface waters using verified Lagrangian sampling.

Contaminants released from wastewater treatment plants can persist in surface waters for substantial distances. Much research has gone into evaluating the fate and transport of these contaminants, but this work has often assumed constant flow from wastewater treatment plants. However, effluent discharge commonly varies widely over a 24-hour period, and this variation controls contaminant loading and can profoundly influence interpretations of environmental data. We show that methodologies relying on the normalization of downstream data to conservative elements can give spurious results, and should not be used unless it can be verified that the same parcel of water was sampled. Lagrangian sampling, which in theory samples the same water parcel as it moves downstream (the Lagrangian parcel), links hydrologic and chemical transformation processes so that the in-stream fate of wastewater contaminants can be quantitatively evaluated. However, precise Lagrangian sampling is difficult, and small deviations - such as missing the Lagrangian parcel by less than 1h - can cause large differences in measured concentrations of all dissolved compounds at downstream sites, leading to erroneous conclusions regarding in-stream processes controlling the fate and transport of wastewater contaminants. Therefore, we have developed a method termed "verified Lagrangian" sampling, which can be used to determine if the Lagrangian parcel was actually sampled, and if it was not, a means for correcting the data to reflect the concentrations which would have been obtained had the Lagrangian parcel been sampled. To apply the method, it is necessary to have concentration data for a number of conservative constituents from the upstream, effluent, and downstream sites, along with upstream and effluent concentrations that are constant over the short-term (typically 2-4h). These corrections can subsequently be applied to all data, including non-conservative constituents. Finally, we show how data from other studies can be corrected.

Chemical loading into surface water along a hydrological, biogeochemical, and land use gradient: a holistic watershed approach.

Identifying the sources and impacts of organic and inorganic contaminants at the watershed scale is a complex challenge because of the multitude of processes occurring in time and space. Investigation of geochemical transformations requires a systematic evaluation of hydrologic, landscape, and anthropogenic factors. The 1160 km2 Boulder Creek Watershed in the Colorado Front Range encompasses a gradient of geology, ecotypes, climate, and urbanization. Streamflow originates primarily as snowmelt and shows substantial annual variation. Water samples were collected along a 70-km transect during spring-runoff and base-flow conditions, and analyzed for major elements, trace elements, bulk organics, organic wastewater contaminants (OWCs), and pesticides. Major-element and trace-element concentrations were low in the headwaters, increased through the urban corridor, and had a step increase downstream from the first major wastewater treatment plant (WWTP). Boron, gadolinium, and lithium were useful inorganic tracers of anthropogenic inputs. Effluent from the WWTP accounted for as much as 75% of the flow in Boulder Creek and was the largest chemical input. Under both hydrological conditions, OWCs and pesticides were detected in Boulder Creek downstream from the WWTP outfall as well as in the headwater region, and loads of anthropogenic-derived contaminants increased as basin population density increased. This report documents a suite of potential endocrine-disrupting chemicals in a reach of stream with native fish populations showing indication of endocrine disruption.