Soluble Reactive Phosphorus Concentrations Research Articles

Characterizing dissolved inorganic and organic nutrients in the oligotrophic Kuroshio Current off eastern Taiwan during warm seasons

This study conducted sensitive and precise analyses of dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) concentrations and trace concentrations of nitrate and nitrite (N+N) and soluble reactive phosphorus (SRP) in seawater. The methods were applied to investigate the distributions and controls of N+N, SRP, DON, and DOP in the oligotrophic Kuroshio Current (KC) area off eastern Taiwan during warm seasons. The water in the studied area was classified into four major types: typical Kuroshio water (KW), KW influenced by the East China Sea water, KC influenced by the South China Sea (SCS) water, and KW influenced by the SCS water and river plumes, which is confined to the coastal zone. Nutrient distributions in KC revealed very low N+N (0.002−0.40 μM) and SRP (0.015−0.125 μM) concentrations but high DON (<8 μM) and DOP (<0.3 μM) concentrations above the nutricline depth, which accounted for >80% of TDN and TDP, respectively; theses concentrations can primarily be attributed to strong, permanent surface stratification. Among the water types, KW had the lowest N+N, SRP, DON, and DOP concentrations but greatest chlorophyll maximum depth and nutricline depth, except for in locations influenced by island-induced upwelling. The concentrations of all nutrients increased by various degrees in the other water types, which was attributed to the exchange and mixing of different water masses and coastal uplift of subsurface waters. KW was not only highly oligotrophic but also N+N-limited reflected from very low [N+N]/[SRP] ratio (0.02−0.15) in the mixed layer (ML). Overall, the N+N limitation and high nitrate anomaly value (N*: 2.47 ± 0.16 μM) above the nutricline depth strongly indicate prevailing N2 fixation at the surface of KW. Very high DON/DOP ratio in KW (16.9−69.1) probably resulted from the release of N-rich organic nutrients from phytoplankton including N2 fixers at the surface and faster recycling of DOP than DON in deep waters. Persistent coastal uplift of subsurface water occurs everywhere over the shore-side region of the KC, resulting in increasing surface concentrations of nutrients and chlorophyll a. Overall, the aforementioned physical and biogeochemical processes determined the upper-ocean distributions of nutrient species in warm seasons.

Predicting river phytoplankton blooms and community succession using ecological niche modeling

AbstractExcessive phytoplankton concentrations in rivers can result in the loss of plant and invertebrate communities, and threaten drinking water supplies. Whilst the physicochemical controls on algal blooms have been identified previously, how these factors combine to control the initiation, size, and cessation of blooms in rivers is not well understood. We applied flow cytometry to quantify diatom, chlorophyte, and cyanobacterial group abundances in the River Thames (UK) at weekly intervals from 2011 to 2022, alongside physicochemical data. A niche modeling approach was used to identify thresholds in water temperature, flow, solar radiation, and soluble reactive phosphorus (SRP) concentrations required to produce periods of phytoplankton growth, with blooms only occurring when all thresholds were met. The thresholds derived from the 2011 to 2018 dataset were applied to a test data set (2019–2022), which predicted the timing and duration of blooms at accuracies of > 80%. Diatoms and nano‐chlorophyte blooms were initiated by flow and water temperature, and usually terminated due to temperature and flow going out of the threshold range, or SRP and Si becoming limiting. Cyanobacterial bloom dynamics were primarily controlled by water temperature and solar radiation. This simple methodology provides a key understanding of phytoplankton community succession and inter‐annual variation and can be applied to any river with similar water quality and phytoplankton data. It provides early warnings of algal and cyanobacterial bloom timings, which support future catchment management decisions to safeguard water resources, and provides a basis for modeling changing phytoplankton bloom risk due to future climate change.

Nutrient structure dynamics and microbial communities at the water-sediment interface in an extremely acidic lake in northern Patagonia.

Lake Caviahue (37° 50 'S and 71° 06' W; Patagonia, Argentina) is an extreme case of a glacial, naturally acidic, aquatic environment (pH ~ 3). Knowledge of the bacterial communities in the water column of this lake, is incipient, with a basal quantification of the bacterioplankton abundance distribution in the North and South Basins of Lake Caviahue, and the described the presence of sulfur and iron oxidizing bacteria in the lake sediments. The role that bacterioplankton plays in nutrient utilization and recycling in this environment, especially in the phosphorus cycle, has not been studied. In this work, we explore this aspect in further depth by assessing the diversity of pelagic, littoral and sediment bacteria, using state of the art molecular methods and identifying the differences and commonalties in the composition of the cognate communities. Also, we investigate the interactions between the sediments of Lake Caviahue and the microbial communities present in both sediments, pore water and the water column, to comprehend the ecological relationships driving nutrient structure and fluxes, with a special focus on carbon, nitrogen, and phosphorus. Two major environmental patterns were observed: (a) one distinguishing the surface water samples due to temperature, Fe2+, and electrical conductivity, and (b) another distinguishing winter and summer samples due to the high pH and increasing concentrations of N-NH4+, DOC and SO42-, from autumn and spring samples with high soluble reactive phosphorus (SRP) and iron concentrations. The largest bacterial abundance was found in autumn, alongside higher levels of dissolved phosphorus, iron forms, and increased conductivity. The highest values of bacterial biomass were found in the bottom strata of the lake, which is also where the greatest diversity in microbial communities was found. The experiments using continuous flow column microcosms showed that microbial growth over time, in both the test and control columns, was accompanied by a decrease in the concentration of dissolved nutrients (SRP and N-NH4+), providing proof that sediment microorganisms are active and contribute significantly to nutrient utilization/mobilization.

Godzilla mineral dust and La Soufrière volcanic ash fallout immediately stimulate marine microbial phosphate uptake

During the “Godzilla” dust storm of June 2020, unusually high fluxes of mineral dust traveled across the Atlantic from the Sahara Desert, reaching the Caribbean Basin, Gulf Coast, and southeastern United States. Additionally, an eruption of the La Soufrière volcano on St. Vincent in April 2021 generated substantial ashfall in the southeastern Caribbean. While many studies have analyzed mineral dust’s ability to relieve nutrient limitation of phosphorus (P) in the P-stressed North Atlantic, less is known about the impact of extreme events and other natural aerosols on fluxes of P into seawater and from seawater into marine microbial cells. We quantified P and iron (Fe) content in mineral dust from the Godzilla dust storm and volcanic ash from the La Soufrière eruption collected at Ragged Point, Barbados. We also performed seawater incubations to assess the marine microbial response to aerosol deposition. Using environmentally-relevant concentrations of atmospheric particles for within the ocean’s mixed layer allowed us to draw realistic conclusions about how these deposition events impacted P cycling in situ. Volcanic ash has lower P content than mineral dust, and P in volcanic ash is far less soluble (~1%) than assumed in current atmospheric deposition models. Adding mineral dust and the volcanic ash leachate in concentrations representing different deposition scenarios increased soluble reactive phosphorus (SRP) concentrations in coastal seawater by ~7-32 nM. Phosphate uptake rate was stimulated in coastal seawater after either mineral dust or volcanic ash deposition at aerosol concentrations relevant to the Godzilla dust event, with ash eliciting the fastest uptake rate. Furthermore, high concentrations of both the mineral dust and volcanic ash led to slightly elevated alkaline phosphatase activity (APA) compared to the relevant controls, indicating higher potential for use of dissolved organic phosphorus (DOP) as a P source. Quantifying these aerosols’ impacts on P cycling is a significant step towards achieving a better understanding of their potential roles in relieving nutrient limitation and fueling the biological carbon pump.

Evaluation of woodchip‐bioditch reactors as a nutrient reduction conservation strategy

AbstractContinued increases in nitrogen and phosphorus loads in waterways cause problems with water quality, impacting human health, the economy, and the environment. To reach nutrient load reduction targets, innovative conservation strategies should be evaluated. This study used oval mesocosms (1.2 m × 0.58 m × 0.58 m) to assess the (1) potential of using woodchip‐bioditch reactors for the mitigation of nitrate (NO3−) and soluble reactive phosphorus (SRP) in agricultural waterways; (2) influence of bioditch reactor orientation (parallel, perpendicular, and hybrid) to flow direction on NO3− and SRP concentrations and loads; and (3) impact of bioditch reactor saturation (dry, intermittently wet, and wet) on NO3− and SRP loads reduction. Woodchip‐bioditch reactors successfully reduced NO3− loads compared to controls (p ⩽ 0.031), but SRP load was sometimes higher in bioditch reactor treatments. No consistent differences were identified between orientation of bioditch reactors and flow direction. The constantly wet treatment had a significantly higher NO3− load reduction than the dry treatment and control (p ⩽ 0.042). Our results indicate the promise of woodchip‐bioditch reactors as a nutrient reduction conservation strategy, although further study of nutrient and greenhouse gas dynamics is needed before widespread implementation.

High-frequency soluble reactive phosphorus in-situ analysis in lakes

High-frequency in-situ monitoring of nutrients in lakes is increasingly becoming relevant to understand event-driven nutrient pulses better. These pulses are essential for phytoplankton development but are usually not captured during conventional sampling programs. In-situ monitoring of nutrients in lakes has been lagging despite the role of nutrients in eutrophication. We evaluated an in-situ wet chemistry soluble reactive phosphorus (SRP) analyzer to establish a methodological basis for high-frequency measurements of SRP. The device (based on the molybdate blue method) was evaluated in laboratory and field tests by comparing it with conventional laboratory analysis. The results of the in-situ analyser during laboratory were similar to the conventional analysis (R2 > 0.995, NSE = 0.989, PBIAS = 8.4 %). Repeated measurements by the in-situ analyzer in a 0.1 mg L-1 test solution had a mean and standard deviation of 0.1005 ± 0.0047 and a MAPE of 3.39, indicating the stability of the measurements. During field tests in a hypertrophic lake with anoxic hypolimnion, the in-situ analyzer SRP concentrations were lower and divergent from the laboratory analysis; due to potential interference of the in-situ analyzer's reagents by sulfides. Under aerobic conditions during field tests, the in-situ P results of a eutrophic, mixed shallow lake were similar to those from water samples analyzed in the laboratory (R2 = 0.562 – 0.812, NSE = 0.397 – 0.707, PBIAS = -8.5 – 24.6 %). There was no difference in SRP concentration among the unfiltered, 0.2 µm, and 10 µm pore size filtered samples; filter pore size did not play a role in the measured SRP concentrations. The in-situ SRP analyzer revealed previously unobserved phenomena, e.g., multiple strongly discontinuous SRP peaks reaching almost 0.1 mg L-1; it therefore, offers a solid methodological basis for high-frequency monitoring of SRP. Incorporating high-frequency in-situ nutrient analysis in lake monitoring provides insights into lakes' short-term nutrient dynamics. Such information is essential for understanding the effects of extreme events like droughts, storms, and heat waves.

Environmental implications of salinity and flooding induced changes in porewater nitrogen and phosphorous dynamics

ABSTRACT This study aimed to investigate the effects of fresh water and seawater flooding on phosphorous (P) and nitrogen (N) dynamics in two calcareous soils (Biscayne and Krome) of South Florida using a 28-day greenhouse flooding experiment. Porewater samples were collected at three depths over four periods (1, 7, 14, and 28 days) of flooding and analyzed for selected water quality parameters. Results showed that seawater-flooded Biscayne soil had a 4.4 fold higher porewater soluble reactive phosphorus (SRP) concentration than freshwater. Additionally, porewater SRP concentration and total phosphorus (TP) in Biscayne soil increased with prolonged flooding duration and column depth. Furthermore, both freshwater and seawater flooding increased porewater NH4 + - N concentration; however, the increase was more pronounced in seawater flooded samples. NH4 + - N concentration also increased with flooding duration. Overall, the study highlights the risks of nutrient leaching from seawater flooded coastal soils that could contribute to the deterioration of surface and groundwater quality.

Microbial interactions strengthen deterministic processes during community assembly in a subtropical estuary

Systematic studies on the assembly process and driving mechanisms of microbial communities in estuaries with diverse seasonal and spatial scales are still limited. In this study, high-throughput sequencing, and microbial network analysis were combined to decipher the impact of environmental changes and biological interactions on the maintenance of microbial diversity patterns in the Jiulong River Estuary (JRE). The results showed that overall, stochastic processes dominated the bacterioplankton community assembly in the estuary, accounting for 49.66–74.78 % of the total. Additionally, bacterioplankton community diversity varied significantly across seasons and subzones. Specifically, the concentration of soluble reactive phosphorus (SRP) in the estuary steadily reduced from winter to summer, and the corresponding bacterioplankton community interactions gradually shifted from the weakest interaction in winter to the strongest in summer. The deterministic processes contributed more than half (50.34 %) to microbial assembly in the summer, but only 25.22 % in winter. Deterministic processes prevailed in the seaward with low SRP concentrations and strong bacterioplankton community interactions, while stochastic processes contributed 70.14 % to the assembly of microbial communities riverward. Biotic and abiotic factors, such as nutrients and microbial interactions, jointly drove the seasonal and spatial patterns of bacterioplankton community assembly, but overall, nutrients played a dominant role. Nevertheless, the contributions of nutrients and microbial interactions were equivalent in spatial assembly processes, albeit nutrients were the primary seasonal driver of the bacterioplankton community assembly process. This study emphasizes the significance of microbial interactions in the bacterioplankton community assemblage. These findings provide new and comprehensive insights into the microbial communities' organization in estuaries.

Application of classification machine learning algorithms for characterizing nutrient transport in a clay plain agricultural watershed

Excess nutrients in surface water and groundwater can lead to water quality deterioration in available water resources. Thus, the classification of nutrient concentrations in water resources has gained significant attention during recent decades. Machine learning (ML) algorithms are considered an efficient tool to describe nutrient loss from agricultural land to surface water and groundwater. Previous studies have applied regression and classification ML algorithms to predict nutrient concentrations in surface water and/or groundwater, or to categorize an output variable using a limited number of input variables. However, there have been no studies that examined the application of different ML classification algorithms in agricultural settings to classify various output variables using a wide range of input variables. In this study, twenty-four ML classification algorithms were implemented on a dataset from three locations within the Upper Parkhill watershed, an agricultural watershed in southern Ontario, Canada. Nutrient concentrations in surface water were classified using geochemical and physical water parameters of surface water and groundwater (e.g., pH), climate and field conditions as the input variables. The performance of these algorithms was evaluated using four evaluation metrics (e.g., classification accuracy) to identify the optimal algorithm for classifying the output variables. Ensemble bagged trees was found to be the optimal ML algorithm for classifying nitrate concentration in surface water (accuracy of 90.9%), while the weighted KNN was the most appropriate algorithm for categorizing the total phosphorus concentration (accuracy of 87%). The ensemble subspace discriminant algorithm gave the highest overall classification accuracy for the concentration of soluble reactive phosphorus and total dissolved phosphorus in surface water with an accuracy of 79.2% and 77.9%, respectively. This study exemplifies that ML algorithms can be used to signify exceedance of recommended concentrations of nutrients in surface waters in agricultural watersheds. Results are useful for decision makers to develop nutrient management strategies.

Nutrient uptake in tropical rivers receiving wastewater treatment plant discharge: High mass removal but low nutrient uptake efficiencies

Wastewater treatment plants (WWTPs) have eliminated many problems related to sewage inputs to aquatic systems. However, the treated effluents still affect river and stream ecosystems. Yet, very limited information is available about the fate of treated effluents in tropical receiving water bodies. Here, we examined the longitudinal changes in ammonium (NH4-N), nitrate (NO3-N), and soluble reactive phosphorus (SRP) concentrations in reaches downstream from chronic WWTP inputs in three receiving rivers in São Paulo state (Southeastern Brazil). The studied WWTPs were not designed or operated to have specific tertiary treatment for nutrient removal at the time of the study. We conducted a total of five sampling campaigns between 2019 and 2021. We applied the nutrient spiraling approach to these high-magnitude nutrient additions to examine net nutrient uptake. Changes in nutrient loads along the reaches were also examined. Overall, nutrient concentrations and loads were considerably increased by WWTP discharges. Net uptake lengths (SW-net) for NO3-N, NH4-N, and SRP ranged from 1.2 to 13.6, 1.5–infinity (uptake coefficient < 0), and 1.2–7.5 km, respectively. Net uptake velocities (Vf-net) varied between 0.7–2.5, −0.4 to 4.1, and 0.2–10.2 mm/min, respectively. Areal net uptake rates (Unet) ranged from 0.78 to 10.7, −20.08–45.8, and 0.18–4.4 g/m2/min for NO3-N, NH4-N, and SRP, respectively. High export (long SW-net) and limited net uptake along the reaches (low Vf-net) indicated that nutrients were transported downstream for long distances without efficient removal (nutrient availability higher than demand) despite the high mass removal (high Unet). These results suggest that the export of nutrients is substantial, potentially creating water quality impairments to downstream ecosystems. Our study highlighted that WWTPs with limited nutrient removal have considerable effects on water chemistry, nutrient cycling and loading in tropical receiving freshwaters.

Innovative receiving phase for Chemcatcher® passive sampler for phosphorus in the water environment: Calibration of sampling rate by water temperature and pH

Passive sampling is a technique for monitoring orthophosphate (PO4-P) in the water environment. Compared with traditional grab sampling followed by PO4-P quantification, kinetic-type passive samplers such as Chemcatcher® express representative concentrations of PO4-P as time-weighted average concentrations (CTWA). They can also potentially evaluate much lower PO4-P concentrations, but the available receiving phases of Chemcatcher® used for PO4-P were extremely limited. We developed a new receiving phase, the PSfZS sheet, comprising a zirconium sulfate–surfactant micelle mesostructure and polysulfone matrix. We examined its performance in terms of PO4-P sorption characteristics, PO4-P selectivity, and PO4-P sampling rate (Rs). Its capacity was adequate (12.0 μg-P/cm2) and selectivity for PO4-P uptake was good. The Rs for PO4-P increased with increasing water temperature (8.1–29.1 °C) and decreasing pH (4.1–9.7) in a laboratory calibration, and ranged from 5.27 × 10−2 L/d to 1.66 × 10−1 L/d. We placed the samplers in a municipal wastewater treatment plant, a shallow eutrophic lake, and an oligotrophic caldera lake. The Rs in the deployment sites was calibrated by monitored water temperature and pH. The estimated CTWA of PO4-P in the municipal wastewater treatment plant was similar to the averaged concentration of soluble reactive phosphorus determined by multiple grab samplings. In the lake deployments, we found that the new sampler can quantify CTWA values of PO4-P below 10 μg/L, and thus it provides more technical monitoring options and contributes to the conservation and management of the water environment.

Cyanobacterial organic matter (COM) positive feedback aggravates lake eutrophication by changing the phosphorus release characteristics of sediments

Phosphorus is a key nutrient that causes eutrophication in lakes. Our investigation of 11 eutrophic lakes found that the concentrations of soluble reactive phosphorus (SRP) in the water column and EPC0 in sediments decreased with aggravated eutrophication. There was a significant negative correlation between the SRP concentrations and eutrophication parameters such as chlorophyll a (Chl-a), total phosphorus (TP) and algal biomass (P < 0.001). In addition, SRP concentrations were significantly affected by EPC0 (P < 0.001), while EPC0 was significantly affected by the content of cyanobacterial organic matter (COM) in sediments (P < 0.001). Based on these findings, we hypothesized that COM can alter the phosphorus release characteristics of sediments, including the phosphorus adsorption parameters of sediment (PAPS) and the phosphorus release rate of sediment (PRRS), thereby stabilizing SRP concentrations at lower levels and rapidly replenishing them when depleted by phytoplankton, which in turn benefits cyanobacteria due to their low SRP adaptation strategies. Simulation experiments were conducted to confirm this hypothesis by adding higher plant OM and COM to sediments. The results showed that all types of OM could significantly increase the maximum phosphorus adsorption capacity (Qmax), but only COM could reduce sediment EPC0 and promote PRRS (P < 0.001). Changes in these parameters (i.e., Qmax, EPC0, and PRRS) resulted in a larger SRP adsorption quantity and faster SRP release rate at low SRP concentrations. This promotes the competitive edge of cyanobacteria due to they have a higher affinity for phosphorus than other algae. As an important component of cyanobacteria, EPS can change the phosphorus release characteristics (i.e., PAPS and PRRS) by reducing sediment particle size and increasing sediment surface functional groups. This study revealed the positive feedback effect of COM accumulation in sediments on lake eutrophication from the perspective of phosphorus release characteristics of sediments, which provides a basic reference for the risk assessment of lake eutrophication.

The development of deep-ocean anoxia in a comprehensive ocean phosphorus model

We analyse a model of the phosphorus cycle in the ocean given by Slomp and Van Cappellen (Biogeosciences 4:155–171, 2007. https://doi.org/10.5194/bg-4-155-2007). This model contains four distinct oceanic boxes and includes relevant parts of the water, carbon and oxygen cycles. We show that the model can essentially be solved analytically, and its behaviour completely understood without recourse to numerical methods. In particular, we show that, in the model, the carbon and phosphorus concentrations in the different ocean reservoirs are all slaved to the concentration of soluble reactive phosphorus in the deep ocean, which relaxes to an equilibrium on a time scale of 180,000 y, and we show that the deep ocean is either oxic or anoxic, depending on a critical parameter which we can determine explicitly. Finally, we examine how the value of this critical parameter depends on the physical parameters contained in the model. The presented methodology is based on tools from applied mathematics and can be used to reduce the complexity of other large, biogeochemical models.

Influence of wetlands on nutrients in headwaters of agricultural catchments

AbstractWe investigated the influence of land cover on nutrient concentrations (295 samples) in headwater streams over a 2‐year period in 10 agriculture‐dominated subcatchments (163–8373 ha) in southern Ontario Canada. In this region, monitoring and research on nutrient dynamics in headwater wetlands is sparse. Our results indicated a significant positive correlation (Pearson coefficient ρ = 0.320) between soluble reactive phosphorus (SRP) in the headwater streams and the percentage of wetlands in these agriculture‐dominated catchments. This result suggests that headwater wetlands, and other wet riparian zones, are key sources of SRP in the headwater streams. Nitrate concentrations were positively correlated with % agricultural land cover (ρ = 0.316), consistent with previous studies, while SRP concentrations were negatively correlated with % agricultural land cover (ρ = −0.325). There was a significant positive correlation between SRP concentrations and discharge in some of the streams. Seasonal SRP trends appear to be closely related to temperature‐dependent seasonal changes in redox conditions, including levels of dissolved O2. Surficial geology had some influence on nitrate concentrations in the streams, which tended to be higher in catchments dominated by glacial till (till terrain), compared to catchments with extensive areas of outwash sand, in addition to till terrain.

Seasonal variation and release of soluble reactive phosphorus in an agricultural upland headwater in central Germany

Abstract. Soluble reactive phosphorus (SRP) concentrations in agricultural headwaters can display pronounced seasonal variability at low flow, often with the highest concentrations occurring in summer. These SRP concentrations often exceed eutrophication levels, but their main sources, spatial distribution, and temporal dynamics are often unknown. The purpose of this study is therefore to differentiate between potential SRP losses and releases from soil drainage, anoxic riparian wetlands, and stream sediments in an agricultural headwater catchment. To identify the dominant SRP sources, we carried out three longitudinal stream sampling campaigns for SRP concentrations and fluxes. We used salt dilution tests and natural 222Rn to determine water fluxes in different sections of the stream, and we sampled for SRP, Fe, and 14C dissolved organic carbon (DOC) to examine possible redox-mediated mobilization from riparian wetlands and stream sediments. The results indicate that a single short section in the upper headwater reach was responsible for most of the SRP fluxes to the stream. Analysis of samples taken under summer low-flow conditions revealed that the stream water SRP concentrations, the fraction of SRP within total dissolved P (TDP), and DOC radiocarbon ages matched those in the groundwater entering the gaining section. Pore water from the stream sediment showed evidence of reductive mobilization of SRP, but the exchange fluxes were probably too small to contribute substantially to SRP stream concentrations. We also found no evidence that shallow flow paths from riparian wetlands contributed to the observed SRP loads in the stream. Combined, the results of this campaign and previous monitoring suggest that groundwater is the main long-term contributor of SRP at low flow, and agricultural phosphorus is largely buffered in the soil zone. We argue that the seasonal variation of SRP concentrations was mainly caused by variations in the proportion of groundwater present in the streamflow, which was highest during summer low-flow periods. Accurate knowledge of the various input pathways is important for choosing effective management measures in a given catchment, as it is also possible that observations of seasonal SRP dilution patterns stem from increased mobilization in riparian zones or from point sources.

Influence of foliar traits, watershed physiography, and nutrient subsidies on stream water quality in the upper midwestern United States

The relationship between nutrient cycling and water quality in mixed-use ecosystems is driven by interactions among biotic and abiotic processes. However, the underlying processes cannot always be directly observed or modeled at broad spatial scales. Numerous empirical studies have employed land use patterns, variations in watershed physiography or disturbance regimes to characterize nutrient export from mixed-use watersheds, but simultaneously disentangling the effects of such factors remains challenging and few models directly incorporate vegetation biochemistry. Here we use structural equation models (SEMs) to assess the relative influence of foliar chemical traits (derived from imaging spectroscopy), watershed physiography, and human land use on the water quality (summer baseflow nitrate-N and soluble reactive phosphorus concentration) in watersheds across the Upper Midwestern United States. We use an SEM to link water quality (stream nitrate-nitrogen and dissolved phosphorus) to foliar retention (AVIRIS-Classic derived foliar traits related to recalcitrance), watershed retention (wetland proportion, MODIS Tasseled Cap Wetness), runoff (agricultural and urban land use), and watershed leakiness (AVIRIS-Classic foliar nitrogen, nitrogen deposition). The SEMs confirmed that variables associated with foliar retention derived from imaging spectroscopy are negatively related to watershed leakiness (standardized path coefficient = −0.892) and positively to watershed retention (standardized path coefficient = 0.705), with features related to watershed retention and runoff exerting the strongest controls on water quality (standardized path coefficients of −0.270 and 0.331 respectively). Comparing forested and agricultural watersheds, we found significantly increased importance of foliar retention to watershed leakiness in forests compared to agriculture (standardized coefficients of −1.004 and −0.764 respectively), with measures of watershed retention more important to runoff and water quality in agricultural watersheds. The results illustrate the capacity of imaging spectroscopy to provide measures of foliar traits that influence nutrient cycling in watersheds. Ultimately, the results may help focus development and restoration policies towards building more resilient landscapes that take into consideration associations among functional traits of vegetation, physiography and climate.

Groundwater characterization of the eastern Minesing Wetlands in support of the endangered Hine’s emerald dragonfly (Somatochlora hineana)

The Minesing Wetlands contain Canada’s only known population of Hine’s emerald dragonfly (HED), a species listed as endangered since 2011. The HED relies on groundwater discharge areas to complete its life cycle and therefore the population is potentially sensitive to changes in groundwater. The goals of this study were to, (1) characterize groundwater discharge to the eastern portion of the Minesing Wetlands, which corresponds to the HED habitat, (2) document any significant changes in groundwater chemistry since a 1998 study, and (3) establish a comprehensive baseline water quality data set to facilitate future comparisons. Consistent with HED habitats in the USA, the chemistry of Minesing Wetlands groundwater was dominated by calcium and bicarbonate. Low groundwater chloride and nitrate concentrations indicated minimal impact from activities such as road salt application and fertilizer use. Nitrate was generally only found at the wetland margin where groundwater springs emerged from the base of the uplands. The dominant form of inorganic nitrogen in wetland groundwater was ammonium (max = 1.5 mg N/L), and soluble reactive phosphorus concentrations were also relatively high (8 to 122 µg/L). The most consistent change in wetland groundwater chemistry between the 1998 study and samples collected in 2015–2017 was that chloride concentrations in 10 of 23 wells increased over time, however the maximum mean well chloride (11.6 mg/L) remained well below the guideline for the protection of aquatic life (120 mg/L). To preserve HED habitat, potential impacts to groundwater need to be considered during land use planning for the recharge area.

Spatio-temporal variability of porewater phosphorus concentrations in streambed sediments of an agricultural stream

Streambed sediment and groundwater represent important stores of soluble reactive phosphorus (SRP) in freshwater catchments yet their contributions to watershed SRP loads remain unclear. This study evaluates the spatio-temporal variability and geochemical and hydrologic controls on porewater SRP in the streambed along an agricultural reach, including the influence of groundwater-surface water interactions. High porewater SRP (>1000 µg/L) and high available sediment-bound SRP were observed in low groundwater discharge zones, specifically in the shallow (≤0.1 m) streambed sediments. Porewater SRP concentrations were linked to iron and possibly manganese redox cycling with more-reducing conditions consistently coinciding with high SRP. Porewater SRP varied temporally but distinct seasonal changes across the stream reach were not observed. A shallow oxic cap that may limit SRP release to the stream was observed in the very shallow streambed but its presence was spatially and temporally discontinuous. Finally, data indicate P-rich shallow streambed sediments are the likely source of the observed high SRP porewater concentrations in the streambed rather than incoming groundwater from the adjacent fields. Overall, the findings highlight the complexity of SRP dynamics in agricultural streambeds and provide insight into processes governing the timing and location of SRP loading streams.

Contrasting activation energies of litter-associated respiration and P uptake drive lower cumulative P uptake at higher temperatures

Abstract. Heterotrophic microbes play key roles in regulating fluxes of energy and nutrients, which are increasingly affected by globally changing environmental conditions such as warming and nutrient enrichment. While the effects of temperature and nutrients on microbial mineralization of carbon have been studied in some detail, much less attention has been given to how these factors are altering uptake rates of nutrients. We used laboratory experiments to simultaneously evaluate the temperature dependence of soluble reactive phosphorus (SRP) uptake and respiration by leaf-litter-associated microbial communities from temperate headwater streams. Additionally, we evaluated the influence of the initial concentration of SRP on the temperature dependence of P uptake. Finally, we used simple simulation models to extrapolate our results and estimate the effect of warming and P availability on cumulative gross uptake. We found that the temperature dependence of P uptake was lower than that of respiration (0.48 vs. 1.02 eV). Further, the temperature dependence of P uptake increased with the initial concentration of SRP supplied, ranging from 0.12 to 0.48 eV over an 11 to 212 µg L−1 gradient in initial SRP concentration. Finally, despite our laboratory experiments showing increases in mass-specific rates of gross P uptake with temperature, our simulation models predict declines in cumulative P uptake with warming, because the increased rates of respiration at warmer temperatures more rapidly depleted benthic carbon substrates and consequently reduced the biomass of the benthic microbial community. Thus, even though mass-specific rates of P uptake were higher at the warmer temperatures, cumulative P uptake was lower over the residence time of a pulsed input of organic carbon. Our results highlight the need to consider the combined effects of warming, nutrient availability, and resource availability and/or magnitude on carbon processing as important controls of nutrient processing in heterotrophic ecosystems.

Agricultural productivity and water quality tradeoffs of winter cover crops at a landscape scale through the lens of remote sensing

A large body of scientific research studying the impacts of cover crops on crop-water-nutrient dynamics has been based on short-term and/or controlled experimental trials without much consideration of the spatial and temporal heterogeneity that typically exists in the working landscape. As such, those findings are difficult to reproduce on working farms. This study is focused on quantifying the long-term impacts of cover crops on both cash crop (corn and soybean) yields and water quality across the Maumee River watershed (MRW) using publicly accessible historic satellite data, from 2009 to 2019, that leverage spatial and temporal variabilities in the agricultural landscape. Corn and soybean yield maps at 30-m resolution were prepared using regression models that integrated satellite images, weather, and county-scale crop yield data. These yield maps were overlaid with 30-m resolution cover crop maps, which were created for the same period using a machine learning classification model using satellite data and ground-truth observations, to quantify yield differences between corn and soybean fields with and without cover crops. The annual variability in winter cover crop area was compared with publicly accessible data on spring nitrate (NO3–N), total phosphorus (TP), and soluble reactive phosphorus (SRP) loads and concentrations, that were collected at multiple water quality monitoring stations within the MRW. During the study period, cover crops, typically showed minimal to negative yield impacts on cash crops, with yield reductions of up to 1.35 ton/ha for corn and 0.24 ton/ha for soybean. However, crop yield variabilities were found to decline with a longer cover crop history. The winter cover crop area within the MRW was found to have water quality impact, with a strong negative correlation with the spring NO3–N concentration (correlation coefficient (R) = −0.70) and loads (R = −0.65) at the MRW outlet. There was a mixed relationship between the cover crop area and P load and concentration, with a positive correlation (R = 0.17) with spring TP concentration and a negative one with spring TP load (R = −0.29), spring SRP concentration (R = −0.30), and spring SRP load (R = −0.40). Similar relationships were also observed across sub-watersheds within the MRW, suggesting that cover crops can be more effective in reducing NO3–N losses compared to P. These findings highlight the importance of using satellite-based remote sensing to improve the understanding of cover crops and their impacts on crop productivity and water quality at a broader scale.