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Subscriber access provided by NASA GODDARD SPACE FLIGHT CTR is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties. Feature What Goes Up Must Come Down: Integrating Air and Water Quality Monitoring for Nutrients Helen M Amos, Chelcy Miniat, Jason A. Lynch, Jana E. Compton, Pamela Templer, Lori Sprague, Denice Marie Shaw, Douglas A. Burns, Anne W. Rea, David R Whitall, Myles Latoya, David Gay, Mark Nilles, John T. Walker, Anita Rose, Jerad Bales, Jeffery Deacon, and Richard Pouyat Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b03504 • Publication Date (Web): 19 Sep 2018 Downloaded from http://pubs.acs.org on September 21, 2018 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

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is published by the American Chemical Society. 1155 Sixteenth Street N.W.,Washington, DC 20036Published by American Chemical Society. Copyright © American Chemical Society.However, no copyright claim is made to original U.S. Government works, or worksproduced by employees of any Commonwealth realm Crown government in the courseof their duties.

Feature

What Goes Up Must Come Down: IntegratingAir and Water Quality Monitoring for Nutrients

Helen M Amos, Chelcy Miniat, Jason A. Lynch, Jana E. Compton, Pamela Templer, Lori Sprague,Denice Marie Shaw, Douglas A. Burns, Anne W. Rea, David R Whitall, Myles Latoya, David

Gay, Mark Nilles, John T. Walker, Anita Rose, Jerad Bales, Jeffery Deacon, and Richard PouyatEnviron. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b03504 • Publication Date (Web): 19 Sep 2018

Downloaded from http://pubs.acs.org on September 21, 2018

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are postedonline prior to technical editing, formatting for publication and author proofing. The American ChemicalSociety provides “Just Accepted” as a service to the research community to expedite the disseminationof scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear infull in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fullypeer reviewed, but should not be considered the official version of record. They are citable by theDigital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,the “Just Accepted” Web site may not include all articles that will be published in the journal. Aftera manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Website and published as an ASAP article. Note that technical editing may introduce minor changesto the manuscript text and/or graphics which could affect content, and all legal disclaimers andethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors orconsequences arising from the use of information contained in these “Just Accepted” manuscripts.

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What Goes Up Must Come Down: Integrating Air and Water Quality Monitoring for 1 Nutrients 2

3 4 Helen M. Amos*†, Chelcy F. Miniat⸹, Jason Lynch§, Jana Compton║, Pamela H. Templer┴, Lori 5 A. Sprague#, Denice Shaw‡, Doug Burns◊, Anne Rea↑, Dave Whitall⸹, LaToya Myles⸹, David 6 Gay₼ , Mark Nilles₼ , John Walker↑, Anita K. Rose⌂, Jerad Bales■, Jeff Deacon₼ , Rich Pouyat₼ 7 8 *

†AAAS Science and Technology Policy Fellow hosted by ‡ 9 ‡U.S. Environmental Protection Agency, Office of Research and Development, Washington, 10 D.C., 20004 11 ₼U.S. Department of Agriculture, Office of the Chief Scientist, Washington, DC, 20250 12 §U.S. Environmental Protection Agency, Office of Air and Radiation, Washington, DC 20004 13 ║U.S. Environmental Protection Agency, Western Ecology Division, Corvallis, OR 97333 14 ┴Boston University, Department of Biology, Boston, MA 02215 15 #U.S. Geological Survey, National Water Quality Program, Denver, CO 80225 16 ◊U.S. Geological Survey, New York Water Science Center, Troy, NY 12309 17 ↑U.S. Environmental Protection Agency, Office of Research and Development, Research 18 Triangle Park, NC 27711 19 ₼National Oceanic and Atmospheric Administration, National Ocean Service, Silver Spring, MD 20 20910 21 ⁑National Oceanic and Atmospheric Administration, Air Resources Laboratory, Oak Ridge, TN 22 37830 23 ₼National Atmospheric Deposition Program, Wisconsin State Laboratory of Hygiene, University 24 of Wisconsin-Madison, Madison, WI, 53706 25 ₼U.S. Geological Survey, National Water Quality Program, Lakewood, CO 80225 26 ⌂U.S. Department of Agriculture Forest Service, Air Resource Management, Washington, DC, 27 20250 28 ■Consortium of Universities for the Advancement Hydrologic Science, Inc., Cambridge, MA 29 02140 30 ₼U.S. Geological Survey, National Water Quality Program, Pembroke, NH 03275 31 ₼U.S. Department of Agriculture Forest Service, Research and Development, Washington, DC 32 20250 33 34

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TOC Art 35

36 37 38 39 40 41 42 43 44 45 46 47 48 49

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Abstract 50 Excess nitrogen and phosphorus (i.e., nutrients) environmental loadings continue to affect 51

ecosystem function and human health across the U.S. Our ability to connect atmospheric inputs 52 of nutrients to aquatic endpoints remains limited due to uncoupled air and water quality 53 monitoring. Where connections exist, the information provides insights about source 54 apportionment, trends, risk to sensitive ecosystems, and efficacy of pollution reduction efforts. 55 We examine several issues driving the need for better integrated monitoring, including: coastal 56 eutrophication, urban hotspots of deposition, a shift from oxidized to reduced nitrogen 57 deposition, and the disappearance of pristine lakes. Successful coordination requires consistent 58 data reporting; collocating deposition and water quality monitoring; improving phosphorous 59 deposition measurements; and filling coverage gaps in urban corridors, agricultural areas, 60 undeveloped watersheds, and coastal zones. 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78

79

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1. Introduction 81

Robust environmental monitoring is fundamental to understanding our environment and 82

assessing the efficacy of environmental policies.1 For many chemical elements of economic and 83

environmental relevance (e.g., nitrogen, phosphorus, sulfur, mercury), air and water chemistry 84

are intrinsically connected. While important progress has been made over the past 20 years,2 85

most monitoring in the U.S. still does not connect atmospheric inputs to surface water quality. 86

Where connected, information from integrated air and surface water quality monitoring has 87

contributed to the basis, justification, and efficacy assessment of the Clean Air Act Amendments 88

of 1990.3 Integrated monitoring at inland sites has helped us understand how decreasing 89

atmospheric nitrogen deposition reduces estuarine nutrient enrichment.4 These efforts have 90

allowed us to determine sources, trends, and whether pollution reduction decisions have been 91

effective and fiscally responsible.5 92

Excess nitrogen and phosphorus (“nutrients”) is one of today’s most challenging and 93

costly water quality issues.6 The challenge arises from balancing trade-offs between human 94

needs, such as food and energy production, with harm to human and ecosystem health, such as 95

drinking water contamination7 or harmful algal blooms and hypoxia.8 Excess nitrogen damages 96

in the U.S. exceed $100 billion annually.9 Despite ongoing source reductions, nutrient 97

enrichment of aquatic ecosystems is difficult to mitigate. The persistent hypoxic zone in the Gulf 98

of Mexico was the size of New Jersey in 2017, the largest in the 15-year record.10 The U.S. 99

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Environmental Protection Agency’s Science Advisory Board recently concluded a national 100

strategy integrating air and water monitoring is needed to understand sources, transport, and fate 101

of excess nutrients.11 102

Atmospheric deposition dominates nitrogen inputs to surface waters over much of the 103

conterminous U.S.12 (Figure 1). Atmospheric deposition physically delivers nitrogen and 104

phosphorus to land and water surfaces by wet (e.g., rain, snow) and dry (e.g., gases and 105

particulates) processes. Even in watersheds with large nutrient sources from agriculture or 106

sewage, atmospheric sources can play an important role depending on land use and timing of 107

runoff.13, 14 It is thus important to quantify atmospheric inputs in order to assess reduction 108

efforts, such as agricultural best practices, water treatment upgrades, and power plant emission 109

caps.4, 15 Fewer than 2% of long-term water quality sites are co-located with nitrogen deposition 110

monitoring in the U.S (Figure 2). Phosphorus is monitored in deposition and water 111

simultaneously at even fewer sites. Recent work reveals the importance of urban atmospheres as 112

a significant potential source of phosphorus to runoff.16 113

Experience from the Acid Rain Program can inform efforts to integrate air and water 114

monitoring at large geographic scales. In the 1970s, studies began documenting widespread 115

acidification of U.S. lakes, streams, and soils.17, 18 Deposition and surface water quality 116

monitoring were coordinated under the Acid Rain Program during the 1990s and 2000s. These 117

sites provided data to assess whether emission reductions from vehicles and the power sector 118

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reduced acidic deposition and improved water quality.3 The number of U.S. lakes and streams at 119

risk for ecological harm from acidity dropped from 24% in 2000 to 9% in 2015,19 estimates that 120

were made possible by merging deposition and water quality monitoring data. 121

122

123

124 Figure 1. (a) Dominant anthropogenic sources of nitrogen to surface water for HUC 8 125 (Hydrologic Unit Code) watersheds. BNF denotes biological nitrogen fixation. (b) Atmospheric 126 nitrogen deposition expressed as a percentage (0 to 100%) of all anthropogenic nitrogen inputs. 127 Source: Compton et al. 20 128 129 130

131

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2. Existing U.S. Atmospheric Deposition and Surface Water Quality Monitoring 132

The primary monitoring network for assessing wet deposition nationally, the National 133

Atmospheric Deposition Program (NADP), was established in 1978. Currently, there are 271 134

NADP sites that analyze sulfate, nitrate, ammonium, base cations, pH, and orthophosphate (as a 135

tracer for contamination) in precipitation. The Clean Air Status and Trends Network 136

(CASTNET) provides continuous, long-term data on dry deposition at 95 sites. Most NADP and 137

CASTNET sites are in rural areas to capture regionally-representative samples. More than 100 138

organizations participate in NADP, conducting their sampling with nationally-consistent 139

methods. The data are primarily used for testing air quality models, providing inputs to 140

watershed models, estimating critical loads of acidity and nitrogen, and developing ecosystem 141

budgets for nitrogen and other elements. NADP and CASTNET monitoring methods do not 142

capture organic forms of nitrogen, which are known to contribute significantly to total nitrogen 143

deposition.21 Better understanding of dry deposition processes and the role of organic nitrogen in 144

deposition budgets are important research needs and are addressed elsewhere.22-24 145

Surface water quality monitoring in the U.S. began in the late 1800s. Today, over 600 146

government agencies, academic institutions, and citizen organizations collect water quality data 147

.25 Water quality constituents associated with deposition include reduced and oxidized nitrogen, 148

pH, alkalinity, sulfate, calcium, phosphorus, mercury, and aluminum. Nutrient data are collected 149

to characterize status and trends, determine whether targets are being met, and investigate factors 150

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affecting water quality. Monitoring locations may be randomly located across a region to provide 151

a statistically representative estimate; or selected to represent certain human activities, 152

environmental settings, or hydrologic conditions to provide an understanding of how, when, and 153

why water quality is changing. 154

At the 2% of locations where deposition and water quality monitoring co-occur, (Figure 155

2), key insights into processing affecting the coupling between deposition and water quality have 156

been documented. For example, long-term co-located monitoring occurs on USDA Forest 157

Service Experimental Forests, such as Coweeta Hydrologic Laboratory and Hubbard Brook 158

Experimental Forests. Multi-decade forest cutting experiments at Coweeta and Hubbard Brook 159

have shown land management can decouple the relationship between atmospheric deposition 160

and stream chemistry until forest regrowth occurs (Hubbard Brook), or for decades following 161

cutting if an atmospheric nitrogen-fixing tree dominates the subsequent forest (Coweeta) (Figure 162

3).26-30 163

Much as it is in the U.S., we know of only limited integrated monitoring in the 164

international community. In Europe, the International Cooperative Program on Integrated 165

Monitoring of Air Pollution Effects on Ecosystems (ICP IM) monitors the effects of air 166

pollutants on ecosystems at 41 sites.31 The Acid Deposition Monitoring Network in East Asia 167

(EANET) is primarily a regional wet deposition network, where 13 countries and 57 sites have 168

recorded wet deposition since 2001 (including nitrate, ammonium, and phosphate as of 2016) 169

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following similar methods to the NADP. EANET organizes quarterly co-located measurements 170

of surface water quality at a subset of sites. There are a few other sites in Asia where long-term 171

measurements of surface water chemistry are integrated with measurements of deposition.32 We 172

are unaware of integrated monitoring networks in South or Central America or Africa. Countries 173

face many of the same scientific and environmental management challenges for nutrients. As 174

such, the motivations for integrated monitoring described here for the U.S. apply elsewhere. 175

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176 Figure 2. Long-term atmospheric deposition and surface water quality nutrient monitoring 177 locations summarized at a HUC-8 level . Depicted are watersheds with: no long-term monitoring 178 sites (grey); only water quality (light blue); only atmospheric deposition (dark blue); both 179 deposition and water quality (yellow); or co-located deposition and water quality monitoring 180 separated by less than 10 km (red). 181

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182

Figure 3. Scatterplots of dissolved inorganic nitrogen (DIN) stream export versus atmospheric 183 deposition at Hubbard Brook and Coweeta before clearcut logging (black), and 10 (red) and 40 184 years (green) after clearcutting. At both sites, clearcutting decoupled the linear pre-logging 185 relationship between deposition and export. The linear coupling eventually recovered at Hubbard 186 Brook, but not at Coweeta due to forest composition and mortality. 187

188 3. Priority Knowledge Gaps Driving Need for Monitoring Coordination 189

190

What is the atmospheric contribution to nutrient enrichment in coastal waters? 191

Excess nutrients in coastal waters can manifest as toxic algal blooms, low oxygen zones, 192

loss of fisheries habitat, and fish kills and can even shift coastal wetlands from sinks to sources 193

of carbon.33 It is a rampant problem across the U.S.,34 Europe,35 and China.36 Atmospheric inputs 194

of nutrients to coastal ecosystems vary widely, ranging from <5% to >60% for nitrogen.37 Due to 195

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a lack of long-term data, empirical estimates exist only for a few eastern U.S. estuaries. There are 196

approximately 30 operating NADP NTN sites and only six CASTNET sites within 25 miles of 197

coastal waters, with none occurring on the West Coast. Currently, there is no national estuarine 198

water quality monitoring program for nutrients. Of the 138 U.S. estuaries,38 many ecologically- 199

and economically-important estuaries have infrequent or no monitoring . The U.S. Geological 200

Survey National Water Quality Network for Rivers and Streams1 has 19 sampling stations 201

located on major rivers, which deliver 65 to 70% of freshwater flowing to the coasts, but over 202

100 U.S. estuaries are still without riverine monitoring. 203

In addition to monitoring upstream sources entering coastal waters, coastal zone 204

monitoring is important, especially for small-to-medium watersheds that can exist entirely within 205

the coastal plain. Deposition to the surface of coastal waters can uniquely impact biology. Most 206

nitrogen deposited to land and transported by rivers will be converted to nitrate or organic 207

nitrogen on its way to the ocean.39 Conversely, direct deposition to coastal waters bypasses the 208

biogeochemical processing of the watershed and can be a significant input of ammonia. A shift 209

in the speciation of nitrogen inputs can result in harmful algal blooms.39 Increasing the number, 210

and coordination, of both wet and dry atmospheric deposition and water quality monitoring sites 211

in coastal zones will help mitigate harmful impacts, preserve healthy coastal ecosystems, and fill 212

data gaps for nutrient fluxes in coastal zones. 213 1 See https://cida.usgs.gov/quality/rivers/coastal.

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214

What is the atmospheric contribution to nutrients in urban stormwater runoff? 215

Elevated deposition has been documented in numerous urban areas, including cities in the 216

U.S.,40-42 Europe,43-45 and Asia.46, 47 Elevated inputs to urban areas can contribute up to 50% of 217

total nitrogen inputs to downstream waters, such as the Chesapeake Bay,48 estimates that are only 218

possible by examining rates of atmospheric deposition with water quality simultaneously. 219

Sources of nitrogen can vary dramatically over the hydrograph, with wastewater sources 220

dominating during base flow and atmospheric deposition increasing during stormflow14. In most 221

urban areas with deposition measurements, they are not coupled to measurements of nutrient 222

loading from other sources to nearby waterways or water quality. This lack of coordination 223

impedes the quantification of atmospheric deposition’s contribution to total nutrient inputs and 224

the evaluation of policies or management options to reduce nutrient loads. Improved 225

coordination in urban areas would enable better decision making related to point and non-point 226

sources of nutrients. 227

228

How is a shift in nitrogen speciation impacting water quality? 229

The U.S. is experiencing a continental-scale shift in the speciation of inorganic nitrogen 230

deposition from oxidized species (nitrogen oxides) to reduced species (ammonia and 231

ammonium).49 Europe50 and China51, 52 are also experiencing long-term trends in the speciation 232

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of inorganic nitrogen deposition, but differ in magnitude and composition from the U.S. 233

Oxidized species are primarily associated with emissions from vehicles and electrical power 234

generation, while reduced species are associated with agricultural activities. U.S. nitrogen oxide 235

emissions declined 67% from 1995 to 2009,3 driven by declining emissions from the 236

transportation and energy sectors. Emissions from food production are projected to increase over 237

coming decades,53 which may continue the increasing proportion of nitrogen deposition from 238

reduced nitrogen species. This change can alter algal community composition and abundance, 239

with some harmful algae preferring reduced nitrogen.54, 55 Algal dynamics are already being 240

altered in western U.S. mountainous lakes, and the problem could become worse with increasing 241

atmospheric inputs of reduced nitrogen.56 242

Recent studies combining ground-based57 and satellite observations58 of reduced forms 243

of nitrogen concentrations and deposition show large spatial and temporal variability within and 244

downwind of agricultural areas, patterns that are not well resolved by current monitoring. 245

Additional NADP Ammonia Monitoring Network (AMoN) and NTN wet deposition sites are 246

needed to fill geographical gaps to characterize reduced nitrogen deposition and trends better, 247

and to improve atmospheric and biogeochemical models that link terrestrial and aquatic nitrogen 248

inputs. Coordinating any expanded monitoring of reduced nitrogen deposition with water 249

monitoring would facilitate decision-making regarding source apportionment, management, and 250

mitigation of affects in aquatic ecosystems. 251

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252

Are atmospheric phosphorous inputs degrading pristine lakes? 253

Phosphorus concentrations in lakes are increasing across the U.S. without a clear 254

explanation.59 An alarming feature of the trend is the decrease in the number of naturally low-255

nutrient concentration lakes from 24.9% in 2007 to 6.7% in 2012.59 Increasing phosphorous 256

concentration in lakes could be driven by increasing atmospheric deposition of phosphorous.60 257

The pH of rainfall has been recovering to less acidic levels since the 1990 Clean Air Act 258

Amendment, which may also be increasing phosphorus solubility in soils.61 259

The current lack of understanding about the extent, or mechanism, for phosphorus 260

deposition to impact surface water quality underscores the need to enhance monitoring 261

coordination. Historically, measuring phosphorus in wet deposition was not a priority given its 262

low concentration in precipitation. For example, in North America, NADP NTN analyzes for 263

orthophosphate (PO43-) in precipitation, but due to protocol limitations, measurable 264

concentrations are observed infrequently and detection is primarily an indication of sample 265

contamination from birds. This is a critical limitation given that trends are strongest in lakes and 266

streams with low phosphorus concentrations. Improved methods are needed for: measuring total, 267

ortho-, organic, and particulate-form phosphorus; and measuring phosphorus in wet and dry 268

deposition. An examination of studies conducted between the mid- to late-1990s through 2007 269

identified only 23 sites worldwide that made measurements of annual wet deposition of 270

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dissolved phosphorus for some of this period. Among atmospheric deposition networks 271

worldwide, only one small network (9 sites), the NADP Atmospheric Integrated Research 272

Monitoring Network (AIRMON) in the eastern U.S., measured it routinely.62 Routine network 273

measurements of both wet and dry phosphorus deposition are needed on all continents and 274

oceans in order to quantify the role of atmospheric deposition in the biogeochemical cycling of 275

phosphorus. Routine co-measurements of comparable phosphorus species in deposition with 276

those measured in lakes and streams will require more coordinated monitoring strategies than are 277

currently in place. 278

279

4. Enhancing Integration 280

Reinvigorating the call for monitoring coordination (e.g., 63, 64) is timely because the 281

computational tools to facilitate integration have never been better and the need – both in terms 282

of filling knowledge gaps and leveraging declining resources – has never been greater. 283

Strategies presented here are informed by today’s problems. We encourage a flexible approach 284

to integration that emphasizes coordination and consistency, and maximizes efficient use of 285

monitoring resources. 286

287

288

Support consistent reporting of surface water quality data and metadata 289

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An important aspect of integrating air and water data is consistency of reporting and 290

metadata. Box 1 provides an example of the obstacles posed by fragmented and inconsistent data 291

documentation, and the challenges in data assimilation. Additional detail about the challenges 292

specific to water data can be found in Sprague et al. 65 We encourage open, online access, 293

sufficient and consistent documentation, and comparable methods for sample collection, 294

analysis, and quality control. The efforts of more than 1,700 U.S. volunteer water monitoring 295

organizations should be included. Consistent and sustained funding – for air and water 296

monitoring – is fundamental. 297

Online infrastructure is needed to support coordination of water data. Launched in 2002, 298

the National Environmental Methods Index (www.nemi.gov) serves as a central clearinghouse 299

for measurement methods and helps users compare methodologies. The Water Quality Portal 300

(www.waterqualitydata.us) provides a single point-of-access to the largest combined water 301

quality data set for groundwater, stream and river, and coastal sites,66 with a consistent metadata 302

documentation format (Water Quality Exchange - WQX).67 These are major steps towards 303

improving compatibility of water and air data. 304

The NADP offers a working model for a federated network of water organizations. 305

Important principles transfer from the NADP model to the coordination of water monitoring for 306

efficient use of increasingly limited resources, such as collaboration among agencies, cost 307

sharing, and centralized online data access. 308

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BOX 1. What “critical loads” teach us about the challenges of data integration 309 A critical load (CL) is a threshold for deposition below which specified ecological 310

changes do not occur in an ecosystem.68 CLs are calculated based on several analytes in water 311 samples. The CL of waterbody is “exceeded” if deposition of a pollutant is too high. CLs inform 312 U.S. air pollution policies, water resource management, and impact assessments for both 313 acidification and nitrogen enrichment. 314

There are many challenges in calculating CLs, particularly at regional-to-national scales. 315 Lynch, Phelan, Pardo and McDonnell 19 could only calculate CLs for approximately 13,000 316 streams and lakes, despite +290 million water quality measurements in our national water quality 317 databases.66 CLs for acidity require nitrate (NO3

-), sulfate (SO4-2), and base cations 318

measurements. Differences in procedures, methods, and reporting can exclude data from 319 assimilation. Another challenge is having all the needed water quality measurements for the 320 same waterbody. In many cases, water samples may only be analyzed for certain analytes (e.g., 321 nitrogen) and not others (e.g., base cations). The new documentation format WQX used by the 322 Water Quality Portal67 provides greater order to unit and naming conventions, fostering better 323 use of water quality data and allowing for better integration with other environmental data, 324 including atmospheric deposition. 325

326 327

Enhance integration at existing monitoring sites 328

Coordination of monitoring networks among organizations is a daunting task, but could 329

be made more tractable by beginning with a pilot effort focused on a specific, small objective. 330

One such objective might be coordinating surface quality water sites co-located with NADP 331

NTN deposition sites, for the purpose of evaluating deposition effects on water quality. A core 332

set of analytes could be identified, either by stakeholders or NADP NTN, and sampled at these 333

sites. A standing committee analogous to the NADP NTN operations committee could facilitate 334

coordination among organizations and establish minimum standards for collection, analyses, and 335

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documentation at co-located sites. Clear procedures for adding new sites to the pilot could ease 336

an eventual transition to an expanded, long-term integration of monitoring with the goal of 337

achieving sufficient coverage to relate air and water quality. 338

In planning pilots, it will be important to consider that atmospheric nitrogen loading to 339

watersheds often, but not always, parallels stream nitrate concentrations.4, 69, 70 Both short- and 340

long-term environmental processes can cause temporal lags between stream water quality and 341

deposition. Fast-growing young forests tend to accumulate nitrogen in biomass, releasing very 342

little to the surface waters, while slower-growing older forests often release nitrogen as their 343

ability to store it diminishes (e.g., nitrogen saturation). Other factors such as snowpack, 344

groundwater storage and flow, and in-lake retention can also attenuate the signal of deposition. 345

The next few years present a critical opportunity to encourage coordination between 346

nutrient water and deposition monitoring. Total deposition samplers for phosphorus are being 347

piloted at 10 to15 NADP sites in the western U.S. beginning in late 2017.71 New in situ sensor 348

technology for measuring nutrients in water is increasingly available at lower prices,72 although 349

care should be exercised not to trade lower up-front costs for higher maintenance and data 350

quality assurance costs. Opportunities for coordination are ripe while organizations are piloting 351

and deploying new technology. We encourage focusing on water quality sites that also measure 352

stream flow. Flow is needed to compare streams of different sizes, quantify exports, and 353

complete nutrient and material budgets. With the frequency of extreme events projected to 354

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increase,73 in situ sensors and co-located monitoring of deposition, surface water quality, and key 355

watershed processes are needed now more than ever. 356

357

Fill monitoring gaps 358

There are regions of the U.S. without long-term deposition or water quality monitoring 359

for nutrients (Figure 2). The most important coverage gaps are: 360

1. Coastal zones. Coordinated air and water monitoring is needed in the Atlantic, Pacific, 361

and Gulf of Mexico. A unique challenge to coastal areas is the need to monitor deposition 362

over open water and in tidal zones, which can be substantially different than deposition 363

inland. Deployment strategies may include buoy systems, use of oil production platforms, 364

or collaboration with local fishers. 365

2. Cities. NADP has recently established sites in Boston, New York, Denver, and the 366

Washington, D.C. area. Additional sites are especially needed in urban corridors with 367

heavy car traffic near waterbodies, such as Charleston and New Orleans. Multiple 368

locations across a single city are ideal because of the heterogeneity of pollution within 369

cities. Where possible, pairing studies of atmospheric deposition in cities to nearby rural 370

areas provides a reference point to quantify potential urban hotspots. 371

3. Agricultural areas. Better deposition and water quality monitoring coverage is needed 372

within and downwind of confined animal feeding operations and intense fertilizer 373

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application in the Midwest and southeastern U.S, including spatially-dense monitoring of 374

atmospheric ammonia concentrations for estimating dry deposition. Fusion of satellite 375

ammonia observations with chemical transport modeling could inform expanded 376

monitoring locations. We note groundwater discharge can also be an important pathway 377

of nutrients in these settings.74 378

4. Undeveloped watersheds. The greatest needs are in the western U.S. and high-elevation 379

areas. Power sources and site maintenance can be logistically challenging in these 380

environments. 381

382

Investment in expanded coordination of new deposition and water quality monitoring 383

locations has benefits for addressing nutrient enrichment, but also builds critical architecture to 384

assess, inform, and respond to emerging and future environmental issues quickly. This could 385

include contamination from other cross-media pollutants such as mercury or organic forms of 386

nitrogen, effects of climate change, effects of large forest fires, or unforeseen consequences of 387

large shifts in major economic sectors such as transportation electrification. The cost of new 388

monitoring is small compared to the potential benefit. Citing an example from the Acid Rain 389

Program, which simultaneously monitored atmospheric deposition and surface water chemistry, 390

“Taken together, the total cost of these critical atmospheric deposition and surface water 391

monitoring programs represents less than 0.4% of the implementation costs of Title IV [of the 392

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Clean Air Act Amendments] and less than 0.01% of the estimated benefits”.1 393

Coordinating atmospheric deposition and surface water quality monitoring will help fill 394

important scientific, management, and policy-relevant knowledge gaps. Monitoring that connects 395

deposition and water quality enables better ecosystem management, evaluation of pollution 396

reduction efforts, and detection and response to unanticipated environmental changes. 397

Investment now in key activities that couple air and water monitoring is not just relevant for 398

nutrients, but has co-benefits for sulfur, mercury, and other pollutants. 399

400

401

Acknowledgements 402 The ideas presented here originate from the spring 2017 expert workshop, Opportunity and 403 Value for Coordinated Nutrient Monitoring: Water, Deposition, and Data Perspectives. This 404 article was developed under Assistance Agreement X3-83588701 awarded by the USEPA to 405 AAAS. Hubbard Brook data were provided by G. Likens28 and funded by NSF LTER (DEB-406 8702331, DEB-9810221, DEB-0423259, DEB-1114804, DEB-1633026, DEB-1637685), and 407 The A. W. Mellon Foundation. Coweeta data were provided by the USDA Forest Service, 408 Southern Research Station, Coweeta Hydrologic Laboratory and supported by NSF LTER (DEB-409 0218001, DEB-0823293, DBI-1226983, DEB-1440485, DEB-1637522). 410 411 Disclaimer 412 The scientific results and conclusions, as well as any views or opinions expressed herein, are 413 those of the author(s) and do not necessarily reflect the views of NOAA or the Department of 414 Commerce, USDA Forest Service, USGS or the Department of the Interior, or the USEPA. 415 416

References 417 418

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Liu, H.; Jin, X.; Xin, Y. J.; Shi, X. K.; Du, E. Z.; Dore, A. J.; Tang, S.; Collett Jr, J. L.; Goulding, 567 K.; Sun, Y. X.; Ren, J.; Zhang, F. S.; Liu, X. J., Quantifying atmospheric nitrogen deposition 568 through a nationwide monitoring network across China. Atmos. Chem. Phys. 2015, 15(21), 569 12345-12360. 570 53. Templer, P. H.; Pinder, R. W.; Goodale, C. L., Effects of nitrogen deposition on 571 greenhouse-gas fluxes for forests and grasslands of North America. Frontiers Ecol. Environ. 572 2012, 10(10), 547-553. 573 54. Donald, D. B.; Bogard, M. J.; Finlay, K.; Leavitt, P. R., Comparative effects of urea, 574 ammonium, and nitrate on phytoplankton abundance, community composition, and toxicity in 575 hypereutrophic freshwaters. Limnol. Ocean. 2011, 56(6), 2161-2175. 576 55. Paerl, H. W.; Boynton, W. R.; Dennis, R. L.; Driscoll, C. T.; Greening, H. S.; Kremer, J. 577 N.; Rabalais, N. N.; Seitzinger, S. P., Atmospheric deposition of nitrogen in coastal waters: 578 Biogeochemical and ecological implications. In Nitrogen loading in coastal water bodies: An 579 atmospheric perspective, American Geophysical Union: 2001; pp 11-52. 580 56. Williams, J. J.; Lynch, J. A.; Saros, J. E.; Labou, S. G., Critical loads of atmospheric N 581 deposition for phytoplankton nutrient limitation shifts in western U.S. mountain lakes. 582 Ecosphere. 2017, 8(10), e01955-n/a. 583 57. Schiferl, L. D.; Heald, C. L.; Van Damme, M.; Clarisse, L.; Clerbaux, C.; Coheur, P. F.; 584 Nowak, J. B.; Neuman, J. A.; Herndon, S. C.; Roscioli, J. R.; Eilerman, S. J., Interannual 585 variability of ammonia concentrations over the United States: Sources and implications. Atmos. 586 Chem. Phys. 2016, 16(18), 12305-12328. 587 58. Warner, J. X.; Dickerson, R. R.; Wei, Z.; Strow, L. L.; Wang, Y.; Liang, Q., Increased 588 atmospheric ammonia over the world's major agricultural areas detected from space. Geophys. 589 Res. Letters. 2017, 44(6), 2875-2884. 590 59. USEPA, National Lakes Assessment 2012: A collaborative survey of lakes in the United 591 States; Washington, DC, 2016. 592 60. Stoddard, J. L.; Van Sickle, J.; Herlihy, A. T.; Brahney, J.; Paulsen, S.; Peck, D. V.; 593 Mitchell, R.; Pollard, A. I., Continental-scale increase in lake and stream phosphorus: Are 594 oligotrophic systems disappearing in the United States? Environ. Sci. Tech. 2016, 50(7), 3409-595 3415. 596 61. Smith, D. R.; Stephensen, M.; King, K. W.; Jarvie, H. P.; Haney, R.; Williams, M. R., A 597 possible trade-off between clean air and clean water. J. Soil Water Conserv. 2017, 72(4), 75A-598 79A. 599 62. Vet, R.; Artz, R. S.; Carou, S.; Shaw, M.; Ro, C.-U.; Aas, W.; Baker, A.; Bowersox, V. 600 C.; Dentener, F.; Galy-Lacaux, C.; Hou, A.; Pienaar, J. J.; Gillett, R.; Forti, M. C.; Gromov, S.; 601 Hara, H.; Khodzher, T.; Mahowald, N. M.; Nickovic, S.; Rao, P. S. P.; Reid, N. W., A global 602 assessment of precipitation chemistry and deposition of sulfur, nitrogen, sea salt, base cations, 603

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