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The effectiveness of multiple small doses of the nitrification inhibitor dicyandiamide (DCD) to decrease denitrification under warm moist conditions was tested in a 1-year field trial on a grazed dairy pasture. DCD was applied approximately every 4 weeks as an aqueous spray onto ten replicate plots 3 days after rotational grazing by dairy cows. Each application was at the rate of 3 kg DCD ha−1, with a total annual application of 33 kg ha−1. Denitrification was assessed 5 days after each DCD application using the acetylene block method. At the end of the trial, the rate of degradation of DCD under summer conditions was measured. DCD significantly decreased the mean annual nitrate concentration by about 17%. Denitrification and denitrification enzyme activity were highly variable and no significant effect of DCD in decreasing denitrification was detected. In the summer month of December, DCD degraded rapidly with an estimated half-life of 5±3 days (mean and standard deviation). [ABSTRACT FROM AUTHOR]

Using data from pastoral soils sampled by horizon at 56 locations across New Zealand, we conducted a meta-analysis. On average, the total depth sampled was 0.93±0.026 m (± SEM), and on a volumetric basis, the total C storage averaged 26.9±1.8, 13.9±0.6 and 9.2±1.4 kg C m−2for allophanic (n=12), non-allophanic (n=40) and pumice soils (n=4), respectively. We estimated the total C storage, and quantified the uncertainty, using the data for samples taken from the uppermost A-horizon whose depth averaged 0.1±0.003 m. For A-horizon samples of the allophanic soils, the mean C content was 108±6 g C kg−1and the bulk density was 772±29 kg m−3, for non-allophanic soils they were 51±4 g C kg−1and 1055±29 kg m−3, and for pumice soils they were 68±9 g C kg−1and 715±45 kg m−3. The C density—a product of the C content and bulk density—of the A-horizon samples was proportional to their air-dried water content, a proxy measure for the mineral surface area. By linear regression with C density of the A-horizon, the total C storage could be estimated with a standard error of 3.1 kg C m−2, 19% of the overall mean. [ABSTRACT FROM AUTHOR]

Environmental warming is thought to alter food web stability and functioning, but whether warming reduces food web resistance and resilience to further climatic events remains surprisingly unexplored. Warming experiments that superimpose acute disturbances are urgently needed to understand how extreme events further threaten the stability and multifunctionality of ecological networks., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Purpose: To evaluate the self-perceived oral health and aesthetics of the dentition and jaw in patients with different types of oral cleft, measured by patient-reported outcome measures (PROMs). Additionally, to compare the results of the PROMs between cleft lip and or/palate (CL/P) patients and non-affected controls., Methods: 420 CL/P patients treated at the cleft team of the Erasmus Medical Center, Rotterdam, The Netherlands, were included, and 138 non-cleft patients were recruited as control-group. Patient's perceptions were retrospectively evaluated using the CLEFT-Q Teeth for dental aesthetics at ages 8, 12 and 22, CLEFT-Q Jaw for jaw aesthetics at ages 12 and 22, and the Child Oral Health Impact Profile-Oral Symptoms Subscale (COHIP-OSS) for oral health at ages 8 and 12. One-way ANOVA was used to compare differences in oral health and aesthetic perceptions among age-groups, cleft types, as well as between cases and controls., Results: CL/P patients were significantly less satisfied than controls with their dental aesthetics (p = 0.001). CL/P patients reported significantly lower satisfaction on CLEFT-Q Teeth scores at ages 8 and 12, than at 22 years (p < 0.001). Patients with the most extensive cleft phenotype, Cleft Lip and Palate (CLAP), reported lowest satisfaction on the CLEFT-Q Teeth. No differences in perceptions of oral health nor in aesthetics of the jaw were found in the different cleft types, ages, nor in study versus control group., Conclusion: This study found differences in self-perceived dental aesthetics: CL/P patients are less satisfied than non-affected controls. CLAP patients are least satisfied, but satisfaction increases with age., (© 2024. The Author(s).)

Denitrifying woodchip bioreactors (DBRs) are an established nitrate mitigation technology, but uncertainty remains on their viability for phosphorus (P) removal due to inconsistent source-sink behaviour in field trials. We investigated whether iron (Fe) redox cycling could be the missing link needed to explain P dynamics in these systems. A pilot-scale DBR (Aotearoa New Zealand) was monitored for the first two drainage seasons (2017-2018), with supplemental in-field measurements of reduced solutes (Fe 2+ , HS - /H 2 S) and their conjugate oxidised species (Fe 3+ /SO 4 2- ) made in 2021 to constrain within-reactor redox gradients. Consistent with thermodynamics, the dissolution of Fe 3+ (s) to Fe 2+ ( aq ) within the DBR sequentially followed O 2 , NO 3 - and MnO 2 (s) reduction, but occurred before SO 4 2- reduction. Monitoring of inlet and outlet chemistry revealed tight coupling between Fe and P (inlet R 2 0.94, outlet R 2 0.85), but distinct dynamics between drainage seasons. In season one, outlet P exceeded inlet P (net P source), and coincided with elevated outlet Fe 2+ , but at ⁓50 % lower P concentrations relative to inlet Fe:P ratios. In season 2 the reactor became a net P sink, coinciding with declining outlet Fe 2+ concentrations (indicating exhaustion of Fe 3+ (s) hydroxides and associated P). In order to characterize P removal under varying source dynamics (i.e. inflows vs in-situ P releases), we used the inlet Fe vs P relationship to estimate P binding to colloidal Fe (hydr)oxide surfaces under oxic conditions, and the outlet Fe 2+ concentration to estimate in-situ P releases associated with Fe (hydr)oxide reduction. Inferred P-removal rates were highest early in season 1 (k = 0.60 g P m 3 d -1 ; 75-100 % removal), declining significantly thereafter (k = 0.01 ± 0.02 g P m 3 d -1 ; ca. 3-67 % removal). These calculations suggest that microbiological P removal in DBRs can occur at comparable magnitudes to nitrate removal by denitrification, depending mainly on P availability and hydraulic retention efficiency., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Many enzymes display non-Arrhenius behavior with curved Arrhenius plots in the absence of denaturation. There has been significant debate about the origin of this behavior and recently the role of the activation heat capacity (Δ C P ⧧ ) has been widely discussed. If enzyme-catalyzed reactions occur with appreciable negative values of Δ C P ⧧ (arising from narrowing of the conformational space along the reaction coordinate), then curved Arrhenius plots are a consequence. To investigate these phenomena in detail, we have collected high precision temperature-rate data over a wide temperature interval for a model glycosidase enzyme MalL, and a series of mutants that change the temperature-dependence of the enzyme-catalyzed rate. We use these data to test a range of models including macromolecular rate theory (MMRT) and an equilibrium model. In addition, we have performed extensive molecular dynamics (MD) simulations to characterize the conformational landscape traversed by MalL in the enzyme-substrate complex and an enzyme-transition state complex. We have crystallized the enzyme in a transition state-like conformation in the absence of a ligand and determined an X-ray crystal structure at very high resolution (1.10 Å). We show (using simulation) that this enzyme-transition state conformation has a more restricted conformational landscape than the wildtype enzyme. We coin the term "transition state-like conformation (TLC)" to apply to this state of the enzyme. Together, these results imply a cooperative conformational transition between an enzyme-substrate conformation (ES) and a transition-state-like conformation (TLC) that precedes the chemical step. We present a two-state model as an extension of MMRT (MMRT-2S) that describes the data along with a convenient approximation with linear temperature dependence of the activation heat capacity (MMRT-1L) that can be used where fewer data points are available. Our model rationalizes disparate behavior seen for MalL and previous results for a thermophilic alcohol dehydrogenase and is consistent with a raft of data for other enzymes. Our model can be used to characterize the conformational changes required for enzyme catalysis and provides insights into the role of cooperative conformational changes in transition state stabilization that are accompanied by changes in heat capacity for the system along the reaction coordinate. TLCs are likely to be of wide importance in understanding the temperature dependence of enzyme activity and other aspects of enzyme catalysis., Competing Interests: The authors declare no competing financial interest., (© 2024 American Chemical Society.)

Quantifying the rate of thermal adaptation of soil microbial respiration is essential in determining potential for carbon cycle feedbacks under a warming climate. Uncertainty surrounding this topic stems in part from persistent methodological issues and difficulties isolating the interacting effects of changes in microbial community responses from changes in soil carbon availability. Here, we constructed a series of temperature response curves of microbial respiration (given unlimited substrate) using soils sampled from around New Zealand, including from a natural geothermal gradient, as a proxy for global warming. We estimated the temperature optima ([Formula: see text]) and inflection point ([Formula: see text]) of each curve and found that adaptation of microbial respiration occurred at a rate of 0.29 °C ± 0.04 1SE for [Formula: see text] and 0.27 °C ± 0.05 1SE for [Formula: see text] per degree of warming. Our results bolster previous findings indicating thermal adaptation is demonstrably offset from warming, and may help quantifying the potential for both limitation and acceleration of soil C losses depending on specific soil temperatures., (© 2023. Springer Nature Limited.)

Climate warming can reduce global soil carbon stocks by enhancing microbial decomposition. However, the magnitude of this loss remains uncertain because the temperature sensitivity of the decomposition of the major fraction of soil carbon, namely resistant carbon, is not fully known. It is now believed that the resistance of soil carbon mostly depends on microbial accessibility of soil carbon with physical protection being the primary control of the decomposition of protected carbon, which is insensitive to temperature changes. However, it is still unclear whether the temperature sensitivity of the decomposition of unprotected carbon, for example, carbon that is not protected by the soil mineral matrix, may depend on the chemical recalcitrance of carbon compounds. In particular, the carbon-quality temperature (CQT) hypothesis asserts that recalcitrant low-quality carbon is more temperature-sensitive to decomposition than labile high-quality carbon. If the hypothesis is correct, climate warming could amplify the loss of unprotected, but chemically recalcitrant, carbon and the resultant CO 2 release from soils to the atmosphere. Previous research has supported this hypothesis based on reported negative relationships between temperature sensitivity and carbon quality, defined as the decomposition rate at a reference temperature. Here we show that negative relationships can arise simply from the arbitrary choice of reference temperature, inherently invalidating those tests. To avoid this artefact, we defined the carbon quality of different compounds as their uncatalysed reaction rates in the absence of enzymes. Taking the uncatalysed rate as the carbon quality index, we found that the CQT hypothesis is not supported for enzyme-catalysed reactions, which showed no relationship between carbon quality and temperature sensitivity. The lack of correlation in enzyme-catalysed reactions implies similar temperature sensitivity for microbial decomposition of soil carbon, regardless of its quality, thereby allaying concerns of acceleration of warming-induced decomposition of recalcitrant carbon., (© 2022 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Diffusive gradients in thin films (DGTs) have been established as useful tools for the determination of nitrate, phosphate, trace metals, and organic concentrations. General use of DGTs, however, is limited by the subsequent requirement for laboratory analysis. To increase the uptake of DGT as a tool for routine monitoring by nonspecialists, not researchers alone, methods for in-field analysis are required. Incorporation of color reagents into the binding layer, or as the binding layer, could enable the easy and accurate determination of analyte concentrations in-field. Here, we sought to develop a chitosan-stabilized silver nanoparticle (AuNP) suspension liquid-binding layer which developed color on exposure to nitrite, combined with an Fe(0)-impregnated poly-2-acrylamido-2-methyl-1-propanesulfonic acid/acrylamide copolymer hydrogel [Fe(0)-p(AMPS/AMA)] for the reduction of nitrate. The AuNP-chitosan suspension was housed in a 3D designed and printed DGT base, with a volume of 2 mL, for use with the standard DGT solution probe caps. A dialysis membrane with a molecular weight cutoff of <15 kDa was used, as part of the material diffusion layer, to ensure that the AuNP-chitosan did not diffuse through to the bulk solution. This synthesized AuNP-chitosan provided quantitative nitrite concentrations (0 to 1000 mg L -1 ) and masses (145 μg) in laboratory-based color development studies. An Fe(III)-impregnated poly-2-acrylamido-2-methyl-1-propanesulfonic acid/acrylamide copolymer hydrogel [Fe(III)-p(AMPS/AMA)] was developed (10% AMPS, and 90% AMA), which was treated with NaBH 4 to form an Fe(0)-p(AMPS/AMA) hydrogel. The Fe(0)-p(AMPS/AMA) hydrogel quantitatively reduced nitrate to nitrite. The total nitrite mass produced was ∼110 μg, from nitrate. The diffusional characteristics of nitrite and nitrate through the Fe(III)-p(AMPS/AMA) and dialysis membrane were 1.40 × 10 -5 and 1.40 × 10 -5 and 5.05 × 10 -6 and 5.15 × 10 -6 cm 2 s -1 at 25 °C respectively. The Fe(0)-hydrogel and AuNP-chitosan suspension operated successfully in laboratory tests individually; however, the combined AuNP-chitosan suspension and Fe(0)-hydrogel DGT did not provide quantitative nitrate concentrations. Further research is required to improve the reaction rate of the AuNP-chitosan nitrite-binding layer, to meet the requirement of rapid binding to operate as a DGT., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Concentrations determined using diffusive gradients in thin films (DGT) have been used to derive time-averaged loads in streams and rivers. However, DGT provide time-weighted average concentrations that assume the independence of concentration and flow. Additionally, dynamic and coordinated changes in temperature, flow, and concentration are potential sources of bias in concentration and load calculations. We modeled scenarios in which temperature and flow were correlated to varying degrees with concentration and evaluated the consequences for DGT concentration and load calculations. As the correlation between solution flow and concentration moved toward 1 and -1, the load determined by DGT either overestimated or underestimated the actual load by as much as 30%. In DGT-based load estimates, the degree of potential bias should be assessed, and the concentration-flow relation should be characterized. As the correlation of analyte concentration and temperature approached 1 and -1, the deviation of the concentration determined by DGT from the actual concentration increased. In most cases, this bias was < 2%; however, if the changes in concentration and temperature were large (∼10 mg L -1 and ∼10 °C), the bias exceeded 5%. Concentration and temperature are unlikely to be perfectly or strongly correlated or anti-correlated in natural systems and thus should not affect the accuracy of DGT concentration calculations in most circumstances. The more solution temperature, flow, and concentration were uncorrelated, the closer DGT-derived concentration and load were to the actual solution concentration and load., (© 2022 The Authors. Journal of Environmental Quality © 2022 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

Climate warming may be exacerbated if rising temperatures stimulate losses of soil carbon to the atmosphere. The direction and magnitude of this carbon-climate feedback are uncertain, largely due to lack of knowledge of the thermal adaptation of the physiology and composition of soil microbial communities. Here, we applied the macromolecular rate theory (MMRT) to describe the temperature response of the microbial decomposition of soil organic matter (SOM) in a natural long-term warming experiment in a geothermally active area in New Zealand. Our objective was to test whether microbial communities adapt to long-term warming with a shift in their composition and their temperature response that are consistent with evolutionary theory of trade-offs between enzyme structure and function. We characterized the microbial community composition (using metabarcoding) and the temperature response of microbial decomposition of SOM (using MMRT) of soils sampled along transects of increasing distance from a geothermally active zone comprising two biomes (a shrubland and a grassland) and sampled at two depths (0-50 and 50-100 mm), such that ambient soil temperature and soil carbon concentration varied widely and independently. We found that the different environments were hosting microbial communities with distinct compositions, with thermophile and thermotolerant genera increasing in relative abundance with increasing ambient temperature. However, the ambient temperature had no detectable influence on the MMRT parameters or the relative temperature sensitivity of decomposition (Q 10 ). MMRT parameters were, however, strongly correlated with soil carbon concentration and carbon:nitrogen ratio. Our findings suggest that, while long-term warming selects for warm-adapted taxa, substrate quality and quantity exert a stronger influence than temperature in selecting for distinct thermal traits. The results have major implications for our understanding of the role of soil microbial processes in the long-term effects of climate warming on soil carbon dynamics and will help increase confidence in carbon-climate feedback projections., (© 2021 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Allophanic tephra-derived soils can sequester sizable quantities of soil organic matter (SOM). However, no studies have visualized the fine internal porous structure of allophanic soil microaggregates, nor studied the carbon structure preserved in such soils or paleosols. We used synchrotron radiation-based transmission X-ray microscopy (TXM) to perform 3D-tomography of the internal porous structure of dominantly allophanic soil microaggregates, and carbon near-edge X-ray absorption fine-structure (C NEXAFS) spectroscopy to characterize SOM in ≤ 12,000-year-old tephra-derived allophane-rich (with minor ferrihydrite) paleosols. The TXM tomography showed a vast network of internal, tortuous nano-pores within an allophanic microaggregate comprising nanoaggregates. SOM in the allophanic paleosols at four sites was dominated by carboxylic/carbonyl functional groups with subordinate quinonic, aromatic, and aliphatic groups. All samples exhibited similar compositions despite differences between the sites. That the SOM does not comprise specific types of functional groups through time implies that the functional groups are relict. The SOM originated at the land/soil surface: ongoing tephra deposition (intermittently or abruptly) then caused the land-surface to rise so that the once-surface horizons were buried more deeply and hence became increasingly isolated from inputs by the surficial/modern organic cycle. The presence of quinonic carbon, from biological processes but vulnerable to oxygen and light, indicates the exceptional protection of SOM and bio-signals in allophanic paleosols, attributable both to the porous allophane (with ferrihydrite) aggregates that occlude the relict SOM from degradation, and to rapid burial by successive tephra-fallout, as well as strong Al-organic chemical bonding. TXM and C NEXAFS spectroscopy help to unravel the fine structure of soils and SOM and are of great potential for soil science studies., (© 2021. The Author(s).)

Diffusive Gradients in Thin-Films (DGT) have traditionally been used to measure time-weighted average concentration in water. We tested whether Br - -DGT in combination with the trace-dilution flow rate method, could be used as a new approach for measuring water flow rate. A novel bromide selective DGT based on the Purolite Bromide Plus anion exchange resin (Br - -DGT) was developed, which provided environmental bromide concentrations comparable to grab samples. The Br - -DGT provided quantitative bromide concentrations at a range of pH, competing ion concentrations, and in synthetic natural solution. The uptake efficiency was 95.7 ± 3.4%, and the elution efficiency was 95.5 ± 4.7%. The absorption maximum/saturation point of each binding disk was 0.684 ± 0.001 mg. Bromide adsorption to the binding layer was linear to 44.1% of the total binding capacity, 0.302 mg. The determined diffusion coefficient through the agarose cross-linked polyacrylamide (APA) hydrogels was 1.05 × 10 -5 cm 2 s -1 at 17.9 °C, temperature corrected to 25 °C was 1.29 × 10 -5 cm 2 s -1 . DGT flow rates were between -14.7 and 6.50% of the flow independently monitored flow rate (weir). In comparison, grab sample flow rates diverged by 5.52 to 58.9% from the weir flow rate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Forest-to-pasture conversion is known to cause global losses in plant and animal diversity, yet impacts of livestock management after such conversion on vital microbial communities in adjoining natural ecosystems remain poorly understood. We examined how pastoral land management practices impact soil microorganisms in adjacent native forest fragments, by comparing bacterial communities sampled along 21 transects bisecting pasture-forest boundaries. Our results revealed greater bacterial taxon richness in grazed pasture soils and the reduced dispersal of pasture-associated taxa into adjacent forest soils when land uses were separated by a boundary fence. Relative abundance distributions of forest-associated taxa (i.e., Proteobacteria and Nitrospirae) and a pasture-associated taxon (i.e., Firmicutes) also suggest a greater impact of pastoral land uses on forest fragment soil bacterial communities when no fence is present. Bacterial community richness and composition were most related to changes in soil physicochemical variables commonly associated with agricultural fertilization, including concentrations of Olsen P, total P, total Cd, delta 15 N and the ratio of C:P and N:P. Overall, our findings demonstrate clear, and potentially detrimental effects of agricultural disturbance on bacterial communities in forest soils adjacent to pastoral land. We provide evidence that simple land management decisions, such as livestock exclusion, can mitigate the effects of agriculture on adjacent soil microbial communities., (© 2021 Society for Applied Microbiology and John Wiley & Sons Ltd.)

Drained peatlands are major sources of CO 2 to the atmosphere, yet the effects of land management and hydrological extremes have been little-studied at spatial scales relevant to agricultural enterprises. We measured fluxes of CO 2 using the eddy covariance (EC) technique at two adjacent dairy farms on a drained peatland in Aotearoa New Zealand with remaining peat depths 5.5-8 m. One site (SD) had shallow surface drains and mean water table depth (WTD) -657 mm, while the other site (BD) had deep field border drains and mean WTD -838 mm. Net ecosystem CO 2 production (NEP) was similar at the two sites when the soils were moist but diverged during late-summer drying, with site BD having 4.56 t C ha -1 greater CO 2 emission than site SD over the four-month dry period. Soil drying reduced gross primary production (GPP) at both sites, while ecosystem respiration (ER) was reduced at site SD but not at site BD. The low dry season respiration rates at site SD contributed to near-zero annual NEP, while higher respiration rates at site BD led to annual CO 2 loss of -4.95 ± 0.59 t C ha -1  yr -1 . Accounting for other imports and exports of carbon, annual net ecosystem carbon balances were -2.23 and -8.47 t C ha -1  yr -1 at sites SD and BD, respectively. It is likely that the contrasting dry season respiration rates resulted from differences in soil physical properties affecting soil moisture vertical redistribution and availability to plants and microbes rather than from the relatively small differences in WTD. These differences could be caused by soil physical disturbances during pasture renewal or paddock recontouring, or time since initial drainage. Therefore, improved soil management might provide practical mitigation against excessive CO 2 emissions during dry conditions, including droughts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The temperature dependence of global photosynthesis and respiration determine land carbon sink strength. While the land sink currently mitigates ~30% of anthropogenic carbon emissions, it is unclear whether this ecosystem service will persist and, more specifically, what hard temperature limits, if any, regulate carbon uptake. Here, we use the largest continuous carbon flux monitoring network to construct the first observationally derived temperature response curves for global land carbon uptake. We show that the mean temperature of the warmest quarter (3-month period) passed the thermal maximum for photosynthesis during the past decade. At higher temperatures, respiration rates continue to rise in contrast to sharply declining rates of photosynthesis. Under business-as-usual emissions, this divergence elicits a near halving of the land sink strength by as early as 2040., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Managed grasslands have the potential to store carbon (C) and partially mitigate climate change. However, it remains difficult to predict potential C storage under a given soil or management practice. To study C storage dynamics due to long-term (1952-2009) phosphorus (P) fertilizer and irrigation treatments in New Zealand grasslands, we measured radiocarbon ( 14 C) in archived soil along with observed changes in C stocks to constrain a compartmental soil model. Productivity increases from P application and irrigation in these trials resulted in very similar C accumulation rates between 1959 and 2009. The ∆ 14 C changes over the same time period were similar in plots that were both irrigated and fertilized, and only differed in a non-irrigated fertilized plot. Model results indicated that decomposition rates of fast cycling C (0.1 to 0.2 year -1 ) increased to nearly offset increases in inputs. With increasing P fertilization, decomposition rates also increased in the slow pool (0.005 to 0.008 year -1 ). Our findings show sustained, significant (i.e. greater than 4 per mille) increases in C stocks regardless of treatment or inputs. As the majority of fresh inputs remain in the soil for less than 10 years, these long term increases reflect dynamics of the slow pool. Additionally, frequent irrigation was associated with reduced stocks and increased decomposition of fresh plant material. Rates of C gain and decay highlight trade-offs between productivity, nutrient availability, and soil C sequestration as a climate change mitigation strategy., Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-021-00838-z., Competing Interests: Conflict of interestThe authors declare that they have no conflict of interest., (© The Author(s) 2021.)

Woodchip bioreactors are a practical, low-cost technology for reducing nitrate (NO 3 ) loads discharged from agriculture. Traditional methods of quantifying their performance in the field mostly rely on low-frequency, time-based (weekly to monthly sampling interval) or flow-weighted sample collection at the inlet and outlet, creating uncertainty in their performance and design by providing incomplete information on flow and water chemistry. To address this uncertainty, two field bioreactors were monitored in the US and New Zealand using high-frequency, multipoint sampling for in situ monitoring of NO 3 -N concentrations. High-frequency monitoring (sub hourly interval) at the inlet and outlet of both bioreactors revealed significant variability in volumetric removal rates and percent reduction, with percent reduction varying by up to 25 percentage points within a single flow event. Time series of inlet and outlet NO 3 showed significant lag in peak concentrations of 1-3 days due to high hydraulic residence time, where calculations from instantaneous measurements produced erroneous estimates of performance and misleading relationships between residence time and removal. Internal porewater sampling wells showed differences in NO 3 concentration between shallow and deep zones, and "hot spot" zones where peak NO 3 removal co-occurred with dissolved oxygen depletion and dissolved organic carbon production. Tracking NO 3 movement through the profile showed preferential flow occurring with slower flow in deeper woodchips, and slower flow further from the most direct flowpath from inlet to outlet. High-frequency, in situ data on inlet and outlet time series and internal porewater solute profiles of this initial work highlight several key areas for future research., (Published by Elsevier Ltd.)

The temperature dependence of biological rates at different scales (from individual enzymes to isolated organisms to ecosystem processes such as soil respiration and photosynthesis) is the subject of much historical and contemporary research. The precise relationship between the temperature dependence of enzyme rates and those at larger scales is not well understood. We have developed macromolecular rate theory (MMRT) to describe the temperature dependence of biological processes at all scales. Here we formalize the scaling relationship by investigating MMRT both at the molecular scale (constituent enzymes) and for growth of the parent organism. We demonstrate that the inflection point ( T inf ) for the temperature dependence of individual metabolic enzymes coincides with the optimal growth temperature for the parent organism, and we rationalize this concordance in terms of the necessity for linearly correlated rates for metabolic enzymes over fluctuating environmental temperatures to maintain homeostasis. Indeed, T inf is likely to be under strong selection pressure to maintain coordinated rates across environmental temperature ranges. At temperatures at which rates become uncorrelated, we postulate a regulatory catastrophe and organism growth rates precipitously decline at temperatures where this occurs. We show that the curvature in the plots of the natural log of the rate versus temperature for individual enzymes determines the curvature for the metabolic process overall and the curvature for the temperature dependence of the growth of the organism. We have called this "the inflection point hypothesis", and this hypothesis suggests many avenues for future investigation, including avenues for engineering the thermal tolerance of organisms.

The increase in environmental nutrient availability as a result of human activities has necessitated the development of mitigation strategies for nutrient removal, such as nitrate. Current methods for determining the efficiency of different mitigation strategies required measurement of changes in nitrate concentrations, however, these methods can be expensive or do not account fully for the temporal variability of nitrate concentration. This study evaluated the utility of Diffusive Gradients in Thins-Films (DGT) for determining nitrate removal in two denitrifying bioreactors, and compared DGT performance to traditional approaches for determining performance, including high and low frequency water grab sampling. The binding layer was produced using the Purolite® A520E anion exchange resin. The uptake and elution efficiencies were 98.8% and 93.4% respectively. DGTs of three material diffusion layer thicknesses were placed in piezometers along longitudinal transects, to enable calculation of the diffusive boundary layer and provide replicates. These were removed after 16, 24 and 36 h, and the accumulated nitrate masses were extracted and quantified to calculate nitrate concentration. Concentrations were subsequently utilised to calculate nitrate removal rates in both bioreactors. Grab samples were taken at 30 and 60 min intervals over those periods, nitrate concentrations were also measured to determine nitrate removal. DGTs provided nitrate removal rates at bioreactor site one (controlled flow, wastewater treatment) of 14.83-30.75 g N m -3  d -1 , and 1.22-3.63 g N m -3  d -1 at site two (variable flow, agricultural run-off). DGT determined nitrate concentrations and removal rates were in strong accordance with high frequency grab sampling, but data collection via DGTs was considerably easier. Utilising DGTs for the measurement of bioreactor performance overcame many of the challenges associated with high frequency grab sampling, and other methods, such as accounting for temporal variation in nitrate concentration and reduced analytical requirements., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Peatland biological, physical and chemical properties change over time in response to alterations in long-term water table position. Such changes complicate our ability to predict the response of peatland carbon stocks to sustained drying. In order to better understand the effect of sustained lowering of the water table on peatland carbon dynamics, we re-visited a drainage-affected bog, repeating eddy covariance measurements of CO 2 flux after a 16-year interval. We found the ecosystem CO 2 sink to have strengthened across the intervening period, despite a deep and fluctuating water table. This was mostly due to an increase in CO 2 uptake through photosynthesis associated with increased shrub growth. We also observed a decline in CO 2 loss through ecosystem respiration. These changes could not be attributed to environmental conditions. Air temperature was the only significant contemporaneous driver of monthly anomalies in CO 2 fluxes, with higher temperatures decreasing the net CO 2 sink via increased ecosystem respiration. However, the effect of air temperature was weak in comparison to the underlying differences between time periods. Therefore, we demonstrate that for drying peatlands, long-term changes within the ecosystem can be of primary importance as drivers of CO 2 exchange. In this peatland, the ecosystem carbon sink has shown resilience to water table drawdown, with internal feedbacks leading to a recovery of the CO 2 sink after a 16-year interval., Competing Interests: Declaration of Competing Interest The authors declare that there is no conflict of interest regarding the publication of this article., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Pastoral agriculture is important for supplying global demand for animal products but pasture productivity is often water limited. Increased plant diversity has been shown to increase water use efficiency (ω) and productivity under water limitation but the optimal mix of species varies spatially, dependent on climate, soil type, and plant water requirements. Consequently, a cost-effective method to screen for high ω plant species and mixes in situ at farm scale is needed. Using carbon isotope discrimination (∆ 13 C) to examine ω is attractive because the method integrates over useful time scales, does not modify the measurement environment, and is cost-effective. Field scale ω was measured using eddy covariance (EC) at two sites with contrasting plant diversity (2 species, 7 species) and compared to the seasonal progression of ω calculated from foliage ∆ 13 C (ω ∆ ). Soil water evaporation (E S ) was removed from EC measured total ecosystem evaporation using a modelling approach and canopy ω (ω C ) was calculated as gross primary production (GPP) divided by canopy evaporation. Mixed species foliage samples were harvested pre-grazing, dried, sub-sampled, ground, and the ratio of 13 C to 12 C was measured. A strong positive correlation was found between ω ∆ and ω C at both study sites (r 2  > 0.83, p < 0.01). In addition to bulk biomass samples, individual species were also harvested seasonally. Relative increases in both ω ∆ and production for some species showed that manipulation of pasture species mixtures may lead to increased ω. Combined with production monitoring, ∆ 13 C could be developed as a tool to optimise species selection for site specific climate and soil conditions to maximise ω and farm production and profit., (Copyright © 2019 Elsevier B.V. All rights reserved.)

High water tables (WT) stabilise peatland carbon (C) through regulation of biogeochemical processes. The impact of peatland WT on ecosystem function, including C exchange, alters over time, and the factors that cause some peatlands to display resilience and others to undergo degradation are poorly understood. Here we use CO 2 flux measurements, measured by eddy covariance, to compare ecosystem function between two raised bogs; one drainage-affected, with a deep and fluctuating water table and the other near-natural, with a shallow and stable water table. The drainage-affected bog was found to be a moderate sink for CO 2 (69 g C m -2  yr -1 ), which was 134 g C m -2  yr -1 less than the near-natural bog (203 g C m -2  yr -1 ). Greater ecosystem productivity has allowed the drainage-impacted bog to act as a CO 2 sink despite higher ecosystem respiration; most likely due to an increase in photosynthetic capacity caused by expansion of ericaceous shrub cover. The tolerance of the vegetation community, particularly the main peat former Empodisma robustum (Restionaceae), to low and fluctuating WT appears to have been key in allowing the site to remain a sink. Despite the current resilience of the ecosystem CO 2 sink, we found gross primary production to be limited under both high and low water tables, even in a year with typical rainfall. This is best explained by the limited physiological ability of ericaceous shrubs to tolerate a fluctuating WT. As such we hypothesise that if the WT continues to drop and become even more unstable, then without further vegetation change, a reduction in gross primary production is likely which may in turn cause the site to become a source for CO 2 ., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Woodchip bioreactors are widely used to control nitrogen export from agriculture using denitrification. There is abundant evidence that drying-rewetting (DRW) cycles can promote enhanced metabolic rates in soils. A 287-d experiment investigated the effects of weekly DRW cycles on nitrate (NO) removal in woodchip columns in the laboratory receiving constant flow of nitrated water. Columns were exposed to continuous saturation (SAT) or to weekly, 8-h drying-rewetting (8 h of aerobiosis followed by saturation) cycles (DRW). Nitrate concentrations were measured at the column outlets every 2 h using novel multiplexed sampling methods coupled to spectrophotometric analysis. Drying-rewetting columns showed greater export of total and dissolved organic carbon and increased NO removal rates. Nitrate removal rates in DRW columns increased by up to 80%, relative to SAT columns, although DRW removal rates decreased quickly within 3 d after rewetting. Increased NO removal in DRW columns continued even after 39 DRW cycles, with ∼33% higher total NO mass removed over each weekly DRW cycle. Data collected in this experiment provide strong evidence that DRW cycles can dramatically improve NO removal in woodchip bioreactors, with carbon availability being a likely driver of improved efficiency. These results have implications for hydraulic management of woodchip bioreactors and other denitrification practices., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

New Zealand agriculture is composed predominantly of pastoral grazing systems; however, forage crops have been increasingly used to supplement the diet of grazing animals. Excreta from grazing animals has been identified as a main contributor of NO emissions. Some forage crops, such as brassicas ( spp.), contain secondary metabolites that have been identified to inhibit soil N cycling processes, and nitrification in particular. Our objective was to determine if secondary metabolites released from brassica tissues inhibited nitrification and reduced NO emissions when incorporated into soil, which was amended with a large amount of urea N (such as derived from urine patches deposited during grazing). Three brassica tissues (kale [ L.], turnip [ L.] bulb, and turnip leaf and stem) and ryegrass ( L.) tissue were incorporated into soil with and without urea solution, and NO, NO, and NH were measured during a 52-d incubation. All brassica tissues reduced urea-derived NO emissions relative to ryegrass tissues when incorporated into soil. According to the mineral N and microbial community data, this reduction, however, could not be attributed to inhibition of nitrification. Although there was less NO from urea in the brassica treatments, total NO emissions increased after incorporation of all tissue residues into soil, so this tradeoff must be explored if brassica tissues are to be considered as a tool for NO reduction., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Temperature is a crucial factor in determining the rates of ecosystem processes, for example, leaf respiration (R) - the flux of plant respired CO 2 from leaves to the atmosphere. Generally, R increases exponentially with temperature and formulations such as the Arrhenius equation are widely used in earth system models. However, experimental observations have shown a consequential and consistent departure from an exponential increase in R. What are the principles that underlie these observed patterns? Here, we demonstrate that macromolecular rate theory (MMRT), based on transition state theory (TST) for enzyme-catalyzed kinetics, provides a thermodynamic explanation for the observed departure and the convergent temperature response of R using a global database. Three meaningful parameters emerge from MMRT analysis: the temperature at which the rate of respiration would theoretically reach a maximum (the optimum temperature, T opt ), the temperature at which the respiration rate is most sensitive to changes in temperature (the inflection temperature, T inf ) and the overall curvature of the log(rate) versus temperature plot (the change in heat capacity for the system, ΔCP‡). On average, the highest potential enzyme-catalyzed rates of respiratory enzymes for R are predicted to occur at 67.0 ± 1.2°C and the maximum temperature sensitivity at 41.4 ± 0.7°C from MMRT. The average curvature (average negative ΔCP‡) was -1.2 ± 0.1 kJ mol -1  K -1 . Interestingly, T opt , T inf and ΔCP‡ appear insignificantly different across biomes and plant functional types, suggesting that thermal response of respiratory enzymes in leaves could be conserved. The derived parameters from MMRT can serve as thermal traits for plant leaves that represent the collective temperature response of metabolic respiratory enzymes and could be useful to understand regulations of R under a warmer climate. MMRT extends the classic TST to enzyme-catalyzed reactions and provides an accurate and mechanistic model for the short-term temperature response of R around the globe., (© 2017 John Wiley & Sons Ltd.)

New Zealand agriculture is predominantly comprised of pastoral grazing systems and deposition of animal excreta during grazing has been identified as a major source of nitrous oxide (N 2 O) emissions. Nitrification inhibitors have been shown to significantly reduce nitrous oxide emissions from grazing pastoral systems, and some plants have been identified as having nitrification inhibiting properties. Brassica crops are one such example as they contain the secondary metabolite glucosinolate (GLS) whose hydrolysis products are thought to slow soil nitrogen cycling. Forage brassicas have been increasingly used to supplement the diet of grazing animals. The aim of this study was to determine if GLS hydrolysis products (phenylethyl isothiocyanate, 4-pent-1-yl isothiocyanate, 2-propenyl nitrile, 2 propenyl isothiocyanate, 4-pentene nitrile) produced in brassica crops reduced N 2 O emissions from soil amended with urea or animal urine. In the laboratory, some GLS hydrolysis products added with urea to soil were found to decrease N 2 O emissions and the most effective product (phenylethyl isothiocyante) reduced N 2 O emissions by 51% during the study. There was some evidence that the reduction in N 2 O emissions found in the lab could be attributed to inhibition of nitrification. Results suggest that the inhibition by GLS hydrolysis products was short-lived and, if considered for use, multiple applications may be necessary to achieve effective inhibition of N 2 O emissions. This reduction, however, was not observed under field conditions. Further investigation is required to test more GLS hydrolysis products to fully understand their impact on N 2 O emissions from urine affected soil., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Globally widespread phosphate fertilizer applications have resulted in long-term increases in the concentration of cadmium (Cd) in soils. The accumulation of this biotoxic, and bioaccumulative metal presents problems for the management of soil-plant-animal systems, because the magnitude and direction of removal fluxes (e.g., crop uptake, leaching) have been difficult to estimate. Here, Cd isotopic compositions (δ 114/110 Cd) of archived fertilizer and soil samples from a 66 year-long agricultural field trial in Winchmore, New Zealand, were used to constrain the Cd soil mass balance between 1959 and 2015 AD, informing future soil Cd accumulation trajectories. The isotopic partitioning of soil Cd sources in this system was aided by a change in phosphate source rocks in 1998 AD, and a corresponding shift in fertilizer isotope composition. The dominant influence of mixing between isotopically distinct Cd end-members was confirmed by a Bayesian modeling approach. Furthermore, isotope mass balance modeling revealed that Cd removal processes most likely increased in magnitude substantially between 2000 and 2015 AD, implying an increase in Cd bioaccumulation and/or leaching over that interval. Natural-abundance stable isotopes are introduced here as a powerful tool for tracing the fate of Cd in agricultural soils, and potentially the wider environment.

The sustainability of using irrigation to produce food depends not only on the availability of sufficient water, but also on the soil's 'response' to irrigation. Stocks of carbon (C) and nitrogen (N) are key components of soil organic matter (SOM), which is important for sustainable agricultural production. While there is some information about the effects of irrigation on soil C stocks in cropping systems, there is a paucity of such studies in pastoral food production systems. For this study, we sampled soils from 34 paired, irrigated and unirrigated pasture sites across New Zealand (NZ) and analysed these for total C and N. On average, irrigated pastures had significantly (P < 0.05) less soil carbon (C) and nitrogen (N) than adjacent unirrigated pastures, with differences of 6.99 t C ha -1 and 0.58 t N ha -1 in the uppermost 0.3 m. Differences in C and N tended to occur throughout the soil profile, so the cumulative differences increased with depth, and the proportion of the soil C lost from deeper horizons was large. There were no relationships between differences in soil C and N stocks and the length of time under irrigation. This study suggests SOM will decrease when pastures under a temperate climate are irrigated. On this basis, increasing the area of temperate pasture land under irrigation would result in more CO 2 in the atmosphere and may directly and indirectly increase N leaching to groundwater. Given the large and increasing area of land being irrigated both in NZ and on a global scale, there is an urgent need to determine whether the results found in this study are also applicable in other regions and under different land management systems (e.g. arable)., (© 2016 John Wiley & Sons Ltd.)

A possible agricultural climate change mitigation option is to increase the amount of soil organic carbon (SOC). Conversely, some factors might lead to inadvertent losses of SOC. Here, we explore the effect of various management options and environmental changes on SOC storage and milk production of dairy pastures in New Zealand. We used CenW 4.1, a process-based ecophysiological model, to run a range of scenarios to assess the effects of changes in management options, plant properties and environmental factors on SOC and milk production. We tested the model by using 2years of observations of the exchanges of water and CO 2 measured with an eddy covariance system on a dairy farm in New Zealand's Waikato region. We obtained excellent agreement between the model and observations, especially for evapotranspiration and net photosynthesis. For the scenario analysis, we found that SOC could be increased through supplying supplemental feed, increasing fertiliser application, or increasing water availability through irrigation on very dry sites, but SOC decreased again for larger increases in water availability. Soil warming strongly reduced SOC. For other changes in key properties, such as changes in soil water-holding capacity and plant root:shoot ratios, SOC changes were often negatively correlated with changes in milk production. The work showed that changes in SOC were determined by the complex interplay between (1) changes in net primary production; (2) the carbon fraction taken off-site through grazing; (3) carbon allocation within the system between labile and stabilised SOC; and (4) changes in SOC decomposition rates. There is a particularly important trade-off between carbon either being removed by grazing or remaining on site and available for SOC formation. Changes in SOC cannot be fully understood unless all four factors are considered together in an overall assessment., (Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.)

Denitrifying bioreactors are organic carbon-filled excavations designed to enhance the natural process of denitrification for the simple, passive treatment of nitrate-nitrogen. Research on and installation of these bioreactors has accelerated within the past 10 years, particularly in watersheds concerned about high nonpoint-source nitrate loads and also for tertiary wastewater treatment. This special section, inspired by the meeting of the Managing Denitrification in Agronomic Systems Community at the 2014 Annual Meeting of the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, aims to firmly establish that denitrifying bioreactors for treatment of nitrate in drainage waters, groundwater, and some wastewaters have moved beyond the proof of concept. This collection of 14 papers expands the peer-reviewed literature of denitrifying bioreactors into new locations, applications, and environmental conditions. There is momentum behind the pairing of wood-based bioreactors with other media (biochar, corn cobs) and in novel designs (e.g., use within treatment trains or use of baffles) to broaden applicability into new kinds of waters and pollutants and to improve performance under challenging field conditions such as cool early season agricultural drainage. Concerns about negative bioreactor by-products (nitrous oxide and hydrogen sulfide emissions, start-up nutrient flushing) are ongoing, but this translates into a significant research opportunity to develop more advanced designs and to fine tune management strategies. Future research must think more broadly to address bioreactor impacts on holistic watershed health and greenhouse gas balances and to facilitate collaborations that allow investigation of mechanisms within the bioreactor "black box.", (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Denitrifying bioreactors using woodchips or other slow-release carbon sources can be an effective method for removing nitrate (NO) from wastewater and tile drainage. However, the ability of these systems to remove fecal microbes from wastewater has been largely uninvestigated. In this study, reductions in fecal indicator bacteria () and viruses (F-specific RNA bacteriophage [FRNA phage]) were analyzed by monthly sampling along a longitudinal transect within a full-scale denitrifying woodchip bioreactor receiving secondary-treated septic tank effluent. Nitrogen, phosphorus, 5-d carbonaceous biochemical oxygen demand (CBOD), and total suspended solids (TSS) reduction were also assessed. The bioreactor demonstrated consistent and substantial reduction of (2.9 log reduction) and FRNA phage (3.9 log reduction) despite receiving highly fluctuating inflow concentrations [up to 3.5 × 10 MPN (100 mL) and 1.1 × 10 plaque-forming units (100 mL) , respectively]. Most of the removal of fecal microbial contaminants occurred within the first meter of the system (1.4 log reduction for ; 1.8 log reduction for FRNA phage). The system was also efficient at removing NO (>99.9% reduction) and TSS (89% reduction). There was no evidence of consistent removal of ammonium, organic nitrogen, or phosphorus. Leaching of CBOD occurred during initial operation but decreased and stabilized at lower values (14 g O m) after 9 mo. We present strong evidence for reliable microbial contaminant removal in denitrifying bioreactors, demonstrating their broader versatility for wastewater treatment. Research on the removal mechanisms of microbial contaminants in these systems, together with the assessment of longevity of removal, is warranted., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Meta-analysis approaches were used in this first quantitative synthesis of denitrifying woodchip bioreactors. Nitrate removal across environmental and design conditions was assessed from 26 published studies, representing 57 separate bioreactor units (i.e., walls, beds, and laboratory columns). Effect size calculations weighted the data based on variance and number of measurements for each bioreactor unit. Nitrate removal rates in bed and column studies were not significantly different, but both were significantly higher than wall studies. In denitrifying beds, wood source did not significantly affect nitrate removal rates. Nitrate removal (mass per volume) was significantly lower in beds with <6-h hydraulic retention times, which argues for ensuring that bed designs incorporate sufficient time for nitrate removal. Rates significantly declined after the first year of bed operation but then stabilized. Nitrogen limitation significantly affected bed nitrate removal. Categorical and linear assessments found significant nitrate removal effects with bed temperature; a of 2.15 was quite similar to other studies. Lessons from this meta-analysis can be incorporated into bed designs, especially extending hydraulic retention times to increase nitrate removal under low temperature and high flow conditions. Additional column studies are warranted for comparative assessments, as are field-based studies for assessing in situ conditions, especially in aging beds, with careful collection and reporting of design and environmental data. Future assessment of these systems might take a holistic view, reviewing nitrate removal in conjunction with other processes, including greenhouse gas and other unfavorable by-product production., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

One of the critical variables that determine the rate of any reaction is temperature. For biological systems, the effects of temperature are convoluted with myriad (and often opposing) contributions from enzyme catalysis, protein stability, and temperature-dependent regulation, for example. We have coined the phrase "macromolecular rate theory (MMRT)" to describe the temperature dependence of enzyme-catalyzed rates independent of stability or regulatory processes. Central to MMRT is the observation that enzyme-catalyzed reactions occur with significant values of ΔCp(‡) that are in general negative. That is, the heat capacity (Cp) for the enzyme-substrate complex is generally larger than the Cp for the enzyme-transition state complex. Consistent with a classical description of enzyme catalysis, a negative value for ΔCp(‡) is the result of the enzyme binding relatively weakly to the substrate and very tightly to the transition state. This observation of negative ΔCp(‡) has important implications for the temperature dependence of enzyme-catalyzed rates. Here, we lay out the fundamentals of MMRT. We present a number of hypotheses that arise directly from MMRT including a theoretical justification for the large size of enzymes and the basis for their optimum temperatures. We rationalize the behavior of psychrophilic enzymes and describe a "psychrophilic trap" which places limits on the evolution of enzymes in low temperature environments. One of the defining characteristics of biology is catalysis of chemical reactions by enzymes, and enzymes drive much of metabolism. Therefore, we also expect to see characteristics of MMRT at the level of cells, whole organisms, and even ecosystems.

We used two years of eddy covariance (EC) measurements collected over an intensively grazed dairy pasture to better understand the key drivers of changes in soil organic carbon stocks. Analysing grazing systems with EC measurements poses significant challenges as the respiration from grazing animals can result in large short-term CO2 fluxes. As paddocks are grazed only periodically, EC observations derive from a mosaic of paddocks with very different exchange rates. This violates the assumptions implicit in the use of EC methodology. To test whether these challenges could be overcome, and to develop a tool for wider scenario testing, we compared EC measurements with simulation runs with the detailed ecosystem model CenW 4.1. Simulations were run separately for 26 paddocks around the EC tower and coupled to a footprint analysis to estimate net fluxes at the EC tower. Overall, we obtained good agreement between modelled and measured fluxes, especially for the comparison of evapotranspiration rates, with model efficiency of 0.96 for weekly averaged values of the validation data. For net ecosystem productivity (NEP) comparisons, observations were omitted when cattle grazed the paddocks immediately around the tower. With those points omitted, model efficiencies for weekly averaged values of the validation data were 0.78, 0.67 and 0.54 for daytime, night-time and 24-hour NEP, respectively. While not included for model parameterisation, simulated gross primary production also agreed closely with values inferred from eddy covariance measurements (model efficiency of 0.84 for weekly averages). The study confirmed that CenW simulations could adequately model carbon and water exchange in grazed pastures. It highlighted the critical role of animal respiration for net CO2 fluxes, and showed that EC studies of grazed pastures need to consider the best approach of accounting for this important flux to avoid unbalanced accounting., (Copyright © 2015. Published by Elsevier B.V.)

Quantifying global patterns of terrestrial nitrogen (N) cycling is central to predicting future patterns of primary productivity, carbon sequestration, nutrient fluxes to aquatic systems, and climate forcing. With limited direct measures of soil N cycling at the global scale, syntheses of the (15)N:(14)N ratio of soil organic matter across climate gradients provide key insights into understanding global patterns of N cycling. In synthesizing data from over 6000 soil samples, we show strong global relationships among soil N isotopes, mean annual temperature (MAT), mean annual precipitation (MAP), and the concentrations of organic carbon and clay in soil. In both hot ecosystems and dry ecosystems, soil organic matter was more enriched in (15)N than in corresponding cold ecosystems or wet ecosystems. Below a MAT of 9.8°C, soil δ(15)N was invariant with MAT. At the global scale, soil organic C concentrations also declined with increasing MAT and decreasing MAP. After standardizing for variation among mineral soils in soil C and clay concentrations, soil δ(15)N showed no consistent trends across global climate and latitudinal gradients. Our analyses could place new constraints on interpretations of patterns of ecosystem N cycling and global budgets of gaseous N loss.

Land-use intensification is a central element in proposed strategies to address global food security. One rationale for accepting the negative consequences of land-use intensification for farmland biodiversity is that it could 'spare' further expansion of agriculture into remaining natural habitats. However, in many regions of the world the only natural habitats that can be spared are fragments within landscapes dominated by agriculture. Therefore, land-sparing arguments hinge on land-use intensification having low spillover effects into adjacent protected areas, otherwise net conservation gains will diminish with increasing intensification. We test, for the first time, whether the degree of spillover from farmland into adjacent natural habitats scales in magnitude with increasing land-use intensity. We identified a continuous land-use intensity gradient across pastoral farming systems in New Zealand (based on 13 components of farmer input and soil biogeochemistry variables), and measured cumulative off-site spillover effects of fertilisers and livestock on soil biogeochemistry in 21 adjacent forest remnants. Ten of 11 measured soil properties differed significantly between remnants and intact-forest reference sites, for both fenced and unfenced remnants, at both edge and interior. For seven variables, the magnitude of effects scaled significantly with magnitude of surrounding land-use intensity, through complex interactions with fencing and edge effects. In particular, total C, total N, δ15N, total P and heavy-metal contaminants of phosphate fertilizers (Cd and U) increased significantly within remnants in response to increasing land-use intensity, and these effects were exacerbated in unfenced relative to fenced remnants. This suggests movement of livestock into surrounding natural habitats is a significant component of agricultural spillover, but pervasive changes in soil biogeochemistry still occur through nutrient spillover channels alone, even in fenced remnants set aside for conservation. These results have important implications for the viability of land-sparing as a strategy for balancing landscape-level conservation and production goals in agricultural landscapes.

Our current understanding of the temperature response of biological processes in soil is based on the Arrhenius equation. This predicts an exponential increase in rate as temperature rises, whereas in the laboratory and in the field, there is always a clearly identifiable temperature optimum for all microbial processes. In the laboratory, this has been explained by denaturation of enzymes at higher temperatures, and in the field, the availability of substrates and water is often cited as critical factors. Recently, we have shown that temperature optima for enzymes and microbial growth occur in the absence of denaturation and that this is a consequence of the unusual heat capacity changes associated with enzymes. We have called this macromolecular rate theory - MMRT (Hobbs et al., , ACS Chem. Biol. 8:2388). Here, we apply MMRT to a wide range of literature data on the response of soil microbial processes to temperature with a focus on respiration but also including different soil enzyme activities, nitrogen and methane cycling. Our theory agrees closely with a wide range of experimental data and predicts temperature optima for these microbial processes. MMRT also predicted high relative temperature sensitivity (as assessed by Q10 calculations) at low temperatures and that Q10 declined as temperature increases in agreement with data synthesis from the literature. Declining Q10 and temperature optima in soils are coherently explained by MMRT which is based on thermodynamics and heat capacity changes for enzyme-catalysed rates. MMRT also provides a new perspective, and makes new predictions, regarding the absolute temperature sensitivity of ecosystems - a fundamental component of models for climate change., (© 2014 John Wiley & Sons Ltd.)

The drainage and conversion of peatlands to productive agro-ecosystems leads to ongoing surface subsidence because of densification (shrinkage and consolidation) and oxidation of the peat substrate. Knowing the ra0te of this surface subsidence is important for future land-use planning, carbon accounting, and economic analysis of drainage and pumping costs. We measured subsidence rates over the past decade at 119 sites across three large, agriculturally managed peatlands in the Waikato region, New Zealand. The average contemporary (2000s-2012) subsidence rate for Waikato peatlands was 19 ± 2 mm yr (± SE) and was significantly less ( = 0.01) than the historic rate of 26 ± 1 mm yr between the 1920s and 2000s. A reduction in the rate of subsidence through time was attributed to the transition from rapid initial consolidation and shrinkage to slower, long-term, ongoing oxidation. These subsidence rates agree well with a literature synthesis of temperate zone subsidence rates reported for similar lengths of time since drainage. A strong nonlinear relationship was found between temperate zone subsidence rates and time since initial peatland drainage: Subsidence (mm yr) = 226 × (years since drained) ( = 0.88). This relationship suggests that time since drainage exerts strong control over the rate of peatland subsidence and that ongoing peatland subsidence rates can be predicted to gradually decline with time in the absence of major land disturbance., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

The increase in enzymatic rates with temperature up to an optimum temperature (Topt) is widely attributed to classical Arrhenius behavior, with the decrease in enzymatic rates above Topt ascribed to protein denaturation and/or aggregation. This account persists despite many investigators noting that denaturation is insufficient to explain the decline in enzymatic rates above Topt. Here we show that it is the change in heat capacity associated with enzyme catalysis (ΔC(‡)p) and its effect on the temperature dependence of ΔG(‡) that determines the temperature dependence of enzyme activity. Through mutagenesis, we demonstrate that the Topt of an enzyme is correlated with ΔC(‡)p and that changes to ΔC(‡)p are sufficient to change Topt without affecting the catalytic rate. Furthermore, using X-ray crystallography and molecular dynamics simulations we reveal the molecular details underpinning these changes in ΔC(‡)p. The influence of ΔC(‡)p on enzymatic rates has implications for the temperature dependence of biological rates from enzymes to ecosystems.

Denitrification beds are containers filled with wood by-products that serve as a carbon and energy source to denitrifiers, which reduce nitrate (NO(3)(-)) from point source discharges into non-reactive dinitrogen (N(2)) gas. This study investigates a range of alternative carbon sources and determines rates, mechanisms and factors controlling NO(3)(-) removal, denitrifying bacterial community, and the adverse effects of these substrates. Experimental barrels (0.2 m(3)) filled with either maize cobs, wheat straw, green waste, sawdust, pine woodchips or eucalyptus woodchips were incubated at 16.8 °C or 27.1 °C (outlet temperature), and received NO(3)(-) enriched water (14.38 mg N L(-1) and 17.15 mg N L(-1)). After 2.5 years of incubation measurements were made of NO(3)(-)-N removal rates, in vitro denitrification rates (DR), factors limiting denitrification (carbon and nitrate availability, dissolved oxygen, temperature, pH, and concentrations of NO(3)(-), nitrite and ammonia), copy number of nitrite reductase (nirS and nirK) and nitrous oxide reductase (nosZ) genes, and greenhouse gas production (dissolved nitrous oxide (N(2)O) and methane), and carbon (TOC) loss. Microbial denitrification was the main mechanism for NO(3)(-)-N removal. Nitrate-N removal rates ranged from 1.3 (pine woodchips) to 6.2 g N m(-3) d(-1) (maize cobs), and were predominantly limited by C availability and temperature (Q(10) = 1.2) when NO(3)(-)-N outlet concentrations remained above 1 mg L(-1). The NO(3)(-)-N removal rate did not depend directly on substrate type, but on the quantity of microbially available carbon, which differed between carbon sources. The abundance of denitrifying genes (nirS, nirK and nosZ) was similar in replicate barrels under cold incubation, but varied substantially under warm incubation, and between substrates. Warm incubation enhanced growth of nirS containing bacteria and bacteria that lacked the nosZ gene, potentially explaining the greater N(2)O emission in warmer environments. Maize cob substrate had the highest NO(3)(-)-N removal rate, but adverse effects include TOC release, dissolved N(2)O release and substantial carbon consumption by non-denitrifiers. Woodchips removed less than half of NO(3)(-) removed by maize cobs, but provided ideal conditions for denitrifying bacteria, and adverse effects were not observed. Therefore we recommend the combination of maize cobs and woodchips to enhance NO(3)(-) removal while minimizing adverse effects in denitrification beds., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Denitrifying woodchip bioreactors (denitrification beds) are increasingly used to remove excess nitrate (NO₃⁻) from point-sources such as wastewater effluent or subsurface drains from agricultural fields. NO₃⁻ removal in these beds is assumed to be due to microbial denitrification but direct measurements of denitrification are lacking. Our objective was to test four different approaches for measuring denitrification rates in a denitrification bed that treated effluent discharged from a glasshouse. We compared these denitrification rates with the rate of NO₃⁻ removal along the length of the bed. The NO₃⁻ removal rate was 8.73 ± 1.45 g m⁻³ d⁻¹. In vitro acetylene inhibition assays resulted in highly variable denitrification rates (DR(AI)) along the length of the bed and generally 5 times greater than the measured (NO₃⁻-N removal rate. An in situ push-pull test, where enriched ¹⁵N-NO₃⁻ was injected into 2 locations along the bed, resulted in rates of 23.2 ± 1.43 g N m⁻³ d⁻¹ and 8.06 ± 1.64 g N m⁻³ d⁻¹. The denitrification rate calculated from the increase in dissolved N₂ and N₂O concentrations (DR(N₂) along the length of the denitrification bed was 6.7 ± 1.61 g N m⁻³ d⁻¹. Lastly, denitrification rates calculated from changes in natural abundance measurements of δ¹⁵N-N₂ and δ¹⁵N-NO₃⁻ along the length of the bed yielded a denitrification rate (DR(NA)) of 6.39 ± 2.07 g m⁻³ d⁻¹. Based on our experience, DR(N₂) measurements were the easiest and most efficient approach for determining the denitrification rate and N₂O production of a denitrification bed. However, the other approaches were useful for testing other hypotheses such as factors limiting denitrification or may be applied to determine denitrification rates in environmental systems different to our study site. DR(N₂) does require very careful sampling to avoid atmospheric N₂ contamination but could be used to rapidly determine denitrification rates in a variety of aquatic systems with high N₂ production and even water flows. These measurements demonstrated that the majority of NO₃⁻ removal was due to heterotrophic denitrification., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

A well-drained soil in N-fertilized dairy pasture was amended with particulate organic carbon (POC), either sawdust or coarse woody mulch, and sampled every 4 wk for a year to test the hypothesis that the addition of POC would increase denitrification activity by increasing the number of microsites where denitrification occurred. Overall mean denitrifying enzyme activity (DEA), on a gravimetric basis, was 100% greater for the woody mulch treatment and 50% greater for the sawdust treatment compared with controls, indicating the denitrifying potential of the soil was enhanced. Despite differences in DEA, no difference in denitrification rate, as measured by the acetylene block technique, was detected among treatments, with an average annual N loss of ∼22 kg N ha yr Soil water content overall was driving denitrification in this well-drained soil as regression of the natural log of volumetric soil water content (VWC) against denitrification rate was highly significant ( = 0.74, < 0.001). Addition of the amendments, however, had significant effects on the availability of both C and N. An additional 20 to 40 kg N ha was stored in POC-amended treatments as a result of increases in the microbial biomass. Basal respiration, as a measure of available C, was 400% greater than controls in the sawdust treatment and 250% greater than controls in the mulch. Net N mineralization, however, was significantly lower in the sawdust treatment, resulting in significantly lower nitrate N levels than in the control. We attribute the lack of measured response in denitrification rate to the high temporal variability in denitrification and suggest that diffusion of nitrate may ultimately have limited denitrification in the amended treatments. Our data indicate that manipulation of denitrification by addition of POC may be possible, particularly when nitrate levels are high, but quantifying differences in the rate of denitrification is difficult because of the temporal nature of the process (particularly the complex interaction of N availability and soil water content)., (American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

Adoption of land-based effluent treatment systems can be constrained by the costs and availability of land. Sufficient land area is needed to ensure nitrate leaching from applied effluent is minimised. One approach to decrease required land area is to enhance N removal by denitrification. Layers of organic matter (100 mm thick) were installed below topsoil of a site irrigated with dairy factory effluent. These "denitrification" layers were tested to determine whether they could decrease nitrate leaching by increasing denitrification. Four plots (10x10 m2 each) were constructed with a denitrification layer installed at 300 mm below the surface, and N losses were measured in leachate using suction cups every 3 weeks for 19 months. N in leachate was compared with 4 control plots. Denitrifying enzyme activity, nitrate concentrations, and carbon availability were measured in samples collected from the denitrification layers. These measurements demonstrated that denitrification occurred in the layer; however, denitrification rates were not sufficiently high to significantly decrease nitrate leaching. Total N leaching was 296 kg N ha(-1) from control plots and 238 kg N ha(-1) from plots with denitrification layers; a total of 798 kg N ha(-1) was applied in effluent. More than 50% of the leached N to 40 cm was as organic N, presumably due to bypass flow. Other studies have demonstrated that thicker denitrification layers (more than 300 mm) can reduce nitrate leaching from small-scale septic tank drainage fields but this study suggests that it is probably not practical to use denitrification layers at larger scales.