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1.
Sci Data ; 11(1): 413, 2024 Apr 22.
Article in English | MEDLINE | ID: mdl-38649341

ABSTRACT

CROPGRIDS is a comprehensive global geo-referenced dataset providing area information for 173 crops for the year 2020, at a resolution of 0.05° (about 5.6 km at the equator). It represents a major update of the Monfreda et al. (2008) dataset (hereafter MRF), the most widely used geospatial dataset previously available, covering 175 crops with reference year 2000 at 10 km spatial resolution. CROPGRIDS builds on information originally provided in MRF and expands it using 27 selected published gridded datasets, subnational data of 52 countries obtained from National Statistical Offices, and the 2020 national-level statistics from FAOSTAT, providing more recent harvested and crop (physical) areas for 173 crops at regional, national, and global levels. The CROPGRIDS data advance the current state of knowledge on the spatial distribution of crops, providing useful inputs for modelling studies and sustainability analyses relevant to national and international processes.


Subject(s)
Crops, Agricultural
3.
Nature ; 620(7976): 1013-1017, 2023 Aug.
Article in English | MEDLINE | ID: mdl-37438527

ABSTRACT

Pesticides are ubiquitous environmental pollutants negatively affecting ecosystem and human health1,2. About 3 Tg of pesticides are used annually in agriculture to protect crops3. How much of these pesticides remain on land and reach the aquifer or the ocean is uncertain. Monitoring their environmental fate is challenging, and a detailed picture of their mobility in time and space is largely missing4. Here, we develop a process-based model accounting for the hydrology and biogeochemistry of the 92 most used agricultural pesticide active substances to assess their pathways through the principal catchments of the world and draw a near-present picture of the global land and river budgets, including discharge to oceans. Of the 0.94 Tg net annual pesticide input in 2015 used in this study, 82% is biologically degraded, 10% remains as residue in soil and 7.2% leaches below the root zone. Rivers receive 0.73 Gg of pesticides from their drainage at a rate of 10 to more than 100 kg yr-1 km-1. By contrast to their fate in soil, only 1.1% of pesticides entering rivers are degraded along streams, exceeding safety levels (concentrations >1 µg l-1) in more than 13,000 km of river length, with 0.71 Gg of pesticide active ingredients released to oceans every year. Herbicides represent the prevalent pesticide residue on both land (72%) and river outlets (62%).


Subject(s)
Agriculture , Environmental Monitoring , Environmental Pollutants , Oceans and Seas , Pesticides , Rivers , Soil , Humans , Ecosystem , Pesticides/analysis , Rivers/chemistry , Soil/chemistry , Water Pollutants, Chemical/analysis , Seawater/chemistry , Herbicides/analysis , Soil Pollutants/analysis , Environmental Pollutants/analysis
4.
Sci Total Environ ; 838(Pt 1): 156011, 2022 Sep 10.
Article in English | MEDLINE | ID: mdl-35595148

ABSTRACT

Microplastic fibres are the most abundant microplastics in waterways worldwide. The settling of fibres is distinct from other particles because of their aspect ratio and shape. In this paper, we test the hypothesis that length, curliness, and settling orientation control the settling velocity of microplastic fibres in a suite of laboratory experiments. Using a Particle Tracking Velocimetry method, we measured the settling velocity of 683 polyester microplastic fibres of 1 to 4 mm in length. Experimental findings support our hypothesis that for microplastic fibre longer than 1 mm, changing settling orientation from horizontal to vertical can increase 1.7 times the settling velocity. Fibre curliness can significantly reduce the settling velocity, where a curly fibre 1.3 times longer than a straight fibre can settle 1.75 times slower. In contrast, short microplastic fibres (less than 1 mm) mostly settle horizontally, and their settling velocity is unaffected by curliness. The drag force exerting on settling microplastic fibres was analysed, and the sphere-equivalent diameter was found to be a good representation of microplastic fibre size to predict the drag coefficient. Measured settling velocity ranges between 0.1 and 0.55 mm/s and exhibits a slight increase with the increasing length of the fibres. This low-velocity range raises concerns that microplastic fibres can favour biological flocculation, form clustered aggregates with microorganisms, feed aquatic organisms and cause bioaccumulation at higher trophic levels.


Subject(s)
Microplastics , Water Pollutants, Chemical , Environmental Monitoring/methods , Particle Size , Plastics/analysis , Water/analysis , Water Pollutants, Chemical/analysis
5.
Sci Data ; 8(1): 263, 2021 10 06.
Article in English | MEDLINE | ID: mdl-34615885

ABSTRACT

We introduce here SOIL-WATERGRIDS, a new dataset of dynamic changes in soil moisture and depth of water table over 45 years from 1970 to 2014 globally resolved at 0.25 × 0.25 degree resolution (about 30 × 30 km at the equator) along a 56 m deep soil profile. SOIL-WATERGRIDS estimates were obtained using the BRTSim model instructed with globally gridded soil physical and hydraulic properties, land cover and use characteristics, and hydrometeorological variables to account for precipitation, ecosystem-specific evapotranspiration, snowmelt, surface runoff, and irrigation. We validate our estimates against independent observations and re-analyses of the soil moisture, water table depth, wetland occurrence, and runoff. SOIL-WATERGRIDS brings into a single product the monthly mean water saturation at three depths in the root zone and the depth of the highest and lowest water tables throughout the reference period, their long-term monthly averages, and data quality. SOIL-WATERGRIDS can therefore be used to analyse trends in water availability for agricultural abstraction, assess the water balance under historical weather patterns, and identify water stress in sensitive managed and unmanaged ecosystems.

6.
Sci Total Environ ; 801: 149731, 2021 Dec 20.
Article in English | MEDLINE | ID: mdl-34438139

ABSTRACT

While the use of pesticides continues to rise worldwide, our understanding of the pervasiveness of associated contamination and the health risks humans may be exposed to remain limited to small samples size, and based on small geographic scales, the exposed population, or the pesticide types. Using our recent mapping of global pesticide use, we quantify three complementary health risk metrics for 92 active ingredients: (i) the pesticide hazard load (PHL); (ii) the population exposure (PE); and (iii) the human intake relative to the acceptable dose (INTR). We integrated these metrics into the pesticide health risk index (PHRI) to assess the standing of 133 nations against the global averages of PHL and PE and the acceptable levels of INTR using data of 2015 (PHRI > 1 indicates a concern). We found that some low-toxicity ingredients have PHL values equivalent to high-toxicity ones, and hence neglecting low-toxicity ingredients may cause biases in risk assessments. The geography of PHL, PE, and INTR show hotspots across the Americas, East and South Asia, and Europe, but with the EU27 countries generally showing lower PHL than other countries possibly due to strict governance on pesticide use. By our measure, about 1.7 billion people (24% of the world population) reside in close proximity to where pesticide applications are greater than 100 kg-a.i. km-2 year-1; about 2.3 billion people (32% of the world population) may exceed the acceptable pesticide intake and about 1.1 billion (15% of the world population) may exceed this by 10 fold. We identified 36 countries with PHRI > 1 and 6 countries with PHRI > 5; of these countries, 10 belong to lower-middle and low income economies. Our analyses show that proximity exposure to pesticides may be more widespread than revealed in occupational studies, and therefore assessments of potential health effects over wider scales may be needed.


Subject(s)
Pesticides , Asia , Europe , Humans , Risk Assessment
7.
Environ Sci Technol ; 54(17): 10399-10410, 2020 09 01.
Article in English | MEDLINE | ID: mdl-32786599

ABSTRACT

Trifluralin is a widely used dinitroaniline herbicide, which can persist in the environment and has substantial ecotoxicity, especially to aquatic organisms. Trifluralin is very insoluble in water (0.22 mg/L at 20 °C) and highly volatile (vapor pressure of 6.7 mPa at 20 °C); these physicochemical properties determine a large part of its environmental fate, which includes rapid loss from soils if surface-applied, strong binding to soil organic matter, and negligible leaching into water. The trifluralin structure contains a tertiary amino group, two nitro-groups and a trifluoromethyl- group. Despite the strongly xenobiotic character of some of these substituents, biodegradation of trifluralin does occur, and pure cultures of bacteria and fungi capable of partially degrading the molecule either by dealkylation or nitro-group reduction have been identified. There are many unanswered questions about the environmental fate and metabolism of this herbicide; the genes and enzymes responsible for biodegradation are largely unknown, the relative roles of abiotic processes vs growth-linked biodegradation vs cometabolism are unresolved, and the impact of different environmental factors on the rates and extents of biodegradation are not clear. Here, we summarize the relevant literature on the persistence and environmental fate of trifluralin with a focus on biodegradation pathways and mechanisms, and we identify the current major knowledge gaps for future research.


Subject(s)
Herbicides , Soil Pollutants , Bacteria , Biodegradation, Environmental , Fungi , Herbicides/analysis , Soil Pollutants/analysis , Trifluralin/analysis
8.
Sci Total Environ ; 717: 137167, 2020 May 15.
Article in English | MEDLINE | ID: mdl-32209264

ABSTRACT

Agricultural pesticides can become persistent environmental pollutants. Among many, glyphosate (GLP) is under particular scrutiny because of its extensive use and its alleged threats to the ecosystem and human health. Here, we introduce the first global environmental contamination analysis of GLP and its metabolite, AMPA, conducted with a mechanistic dynamic model at 0.5 × 0.5° spatial resolution (about 55 km at the equator) fed with geographically-distributed agricultural quantities, soil and biogeochemical properties, and hydroclimatic variables. Our analyses reveal that about 1% of croplands worldwide (385,000 km2) are susceptible to mid to high contamination hazard and less than 0.1% has a high hazard. Hotspots found in South America, Europe, and East and South Asia were mostly correlated to widespread GLP use in pastures, soybean, and corn; diffuse contributing processes were mainly biodegradation recalcitrance and persistence, while soil residue accumulation and leaching below the root zone contributed locally to the hazard in hotspots. Hydroclimatic and soil variables were major controlling factors of contamination hotspots. The relatively low risk of environmental exposure highlighted in our work for a single active substance does not rule out a greater recognition of environmental pollution by pesticides and calls for worldwide cooperation to develop timely standards and implement regulated strategies to prevent excess global environmental pollution.

9.
PLoS One ; 15(2): e0228209, 2020.
Article in English | MEDLINE | ID: mdl-32012181

ABSTRACT

Degraded plastic debris has been found in nearly all waters within and nearby urban developments as well as in the open oceans. Natural removal of suspended microplastics (MPs) by deposition is often limited by their excess buoyancy relative to water, but this can change with the attachment of biological matter. The extent to which the attached biological ballast affects MP dynamics is still not well characterised. Here, we experimentally demonstrate using a novel OMCEC (Optical Measurement of CEll colonisation) system that the biological fraction of MP aggregates has substantial control over their size, shape and, most importantly, their settling velocity. Polyurethane MP aggregates made of 80% biological ballast had an average size almost twice of those containing 5% biological ballast, and sank about two times slower. Based on our experiments, we introduce a settling velocity equation that accounts for different biological content as well as the irregular fractal structure of MP aggregates. This equation can capture the settling velocity of both virgin MPs and microbial-associated MP aggregates in our experiment with 7% error and can be used as a preliminary tool to estimate the vertical transport of MP aggregates made of different polymers and types of microbial ballast.


Subject(s)
Microplastics/metabolism , Water Microbiology , Water/chemistry , Algorithms , Biodegradation, Environmental , Microplastics/chemistry , Microplastics/isolation & purification , Models, Theoretical
10.
Sci Data ; 6(1): 170, 2019 09 12.
Article in English | MEDLINE | ID: mdl-31515508

ABSTRACT

Available georeferenced environmental layers are facilitating new insights into global environmental assets and their vulnerability to anthropogenic inputs. Geographically gridded data of agricultural pesticides are crucial to assess human and ecosystem exposure to potential and recognised toxicants. However, pesticides inventories are often sparse over time and by region, mostly report aggregated classes of active ingredients, and are generally fragmented across local or government authorities, thus hampering an integrated global analysis of pesticide risk. Here, we introduce PEST-CHEMGRIDS, a comprehensive database of the 20 most used pesticide active ingredients on 6 dominant crops and 4 aggregated crop classes at 5 arc-min resolution (about 10 km at the equator) projected from 2015 to 2025. To estimate the global application rates of specific active ingredients we use spatial statistical methods to re-analyse the USGS/PNSP and FAOSTAT pesticide databases along with other public inventories including global gridded data of soil physical properties, hydroclimatic variables, agricultural quantities, and socio-economic indices. PEST-CHEMGRIDS can be used in global environmental modelling, assessment of agrichemical contamination, and risk analysis.

11.
Sci Total Environ ; 658: 105-115, 2019 Mar 25.
Article in English | MEDLINE | ID: mdl-30572210

ABSTRACT

Glyphosate (GLP) is one of the most widely-used herbicides globally and its toxicity to humans and the environment is controversial. GLP is biodegradable, but little is known about the importance of site exposure history and other environmental variables on the rate and pathway of biodegradation. Here, GLP was added to microcosms of soils and sediments with different exposure histories and these were incubated with amendments of glucose, ammonium, and phosphate. GLP concentrations were measured with a newly-developed HPLC method capable of tolerating high concentrations of ammonium and amino acids. GLP biodegradation occurred after a lag-time proportional to the level of GLP pre-exposure in anthropogenically-impacted samples (soils and sediments), while no degradation occurred in samples from a pristine sediment after 180 days of incubation. Exposure history did not influence the rate of GLP degradation, after the lag-time was elapsed. Addition of C, N, and P triggered GLP degradation in pristine sediment and shortened the lag-time before degradation in other samples. In all microcosms, GLP was metabolised into aminomethylphosphonic acid (AMPA), which was highly persistent, and thus appears to be a more problematic pollutant than GLP. Bacterial communities changed along the gradients of anthropogenic impacts, but in some cases, taxonomically very-similar communities showed dramatically different activities with GLP. Our findings reveal important interactions between agriculturally-relevant nutrients and herbicides.


Subject(s)
Biodegradation, Environmental , Geologic Sediments/chemistry , Glycine/analogs & derivatives , Herbicides/metabolism , Soil Pollutants/metabolism , Soil/chemistry , Glycine/analysis , Glycine/metabolism , Herbicides/analysis , Kinetics , Models, Chemical , Soil Microbiology , Soil Pollutants/analysis , Glyphosate
12.
Water Res ; 146: 37-54, 2018 12 01.
Article in English | MEDLINE | ID: mdl-30223108

ABSTRACT

Biodegradation of glyphosate (GLP) and its metabolite aminomethylphosphonic acid (AMPA) was numerically assessed for a vineyard and a wheat field in the Po Valley, Italy. Calculation of the Hazard Quotient suggested that GLP and AMPA can pose a risk of aquifer contamination in the top 1.5 m depth within 50 years of GLP use. Numerical results relative to soil GLP and AMPA concentrations, and GLP age, half life, and turnover time show that GLP was equivalently removed through hydrolysis and oxidation, but the latter produced AMPA. Biodegradation processes in the root zone removed more than 90% of applied GLP and more than 23% of the produced AMPA between two consecutive applications. Doubling organic carbon availability enhanced GLP and AMPA biodegradation, especially GLP hydrolysis to sarcosine. This work highlights that GLP and AMPA removal is controlled by soil water dynamics that depend on ecohydrological boundary conditions, and by carbon sources availability to biodegraders.


Subject(s)
Groundwater , Herbicides , Farms , Glycine/analogs & derivatives , Italy , Triticum , Glyphosate
13.
Sci Total Environ ; 643: 1387-1399, 2018 Dec 01.
Article in English | MEDLINE | ID: mdl-30189555

ABSTRACT

The genesis of suspended aggregates in aquatic ecosystems is not only a result of hydrodynamic mineral interactions but also a complex microbial food web network. A microbiological-physical model (BFLOC2) is introduced here to predict aggregate geometry and settling velocity under simultaneous effects of hydrodynamic and biological processes. While minerals can contribute to aggregate dynamics through collision, aggregation, and breakup, living microorganisms can colonize and establish food web interactions that involve growth and grazing, and modify the aggregate structure. The BFLOC2 model describes the aggregate dynamics resulting from interactions between minerals and three types of microorganisms, namely bacteria, flagellates, and ciliates. BFLOC2 was first calibrated against the size and capacity (fractal) dimension of aggregates formed in a pure mineral system at different mineral concentrations and fluid shear rates, and then against the abundance of aggregate-attached cells in a pure microbial environment. BFLOC2 model and calibrated parameters were then tested against biomineral aggregate size, capacity dimension, and biomass fraction formed in biomineral flocculation experiments at four nutrient concentrations. Modelling of biomineral aggregate dynamics over a wide range of environmental conditions showed that maximum aggregate size, biomass fraction, and settling velocity could occur at different optimal environmental conditions. Unlike mineral aggregates, which have maximum size when shear rate tends to zero, a relative maximum size of biomineral aggregates can be reached at intermediate shear rates as a result of microbiological processes. The settling velocity was ultimately controlled by aggregate size, capacity dimension, and biomass fraction. Microorganism dynamics including cell motility and food web network interactions significantly controlled aggregate-attached cell abundance and aggregate dynamics.


Subject(s)
Environmental Monitoring , Food Chain , Biomass , Flocculation , Fractals , Models, Theoretical
14.
Life Sci Space Res (Amst) ; 17: 1-14, 2018 May.
Article in English | MEDLINE | ID: mdl-29753408

ABSTRACT

A soil-based cropping unit fuelled with human urine for long-term manned space missions was investigated with the aim to analyze whether a closed-loop nutrient cycle from human liquid wastes was achievable. Its ecohydrology and biogeochemistry were analysed in microgravity with the use of an advanced computational tool. Urine from the crew was used to supply primary (N, P, and K) and secondary (S, Ca and Mg) nutrients to wheat and soybean plants in the controlled cropping unit. Breakdown of urine compounds into primary and secondary nutrients as well as byproduct gases, adsorbed, and uptake fractions were tracked over a period of 20 years. Results suggested that human urine could satisfy the demand of at least 3 to 4 out of 6 nutrients with an offset in pH and salinity tolerable by plants. It was therefore inferred that a urine-fuelled life support system can introduce a number of advantages including: (1) recycling of liquids wastes and production of food; (2) forgiveness of neglect as compared to engineered electro-mechanical systems that may fail under unexpected or unplanned conditions; and (3) reduction of supply and waste loads during space missions.


Subject(s)
Glycine max/growth & development , Life Support Systems/instrumentation , Soil/chemistry , Space Flight , Triticum/growth & development , Urine/chemistry , Humans , Space Flight/instrumentation , Waste Management/methods , Workforce
15.
Sci Rep ; 7(1): 3320, 2017 06 12.
Article in English | MEDLINE | ID: mdl-28607347

ABSTRACT

The detection of microbial colonization in geophysical systems is becoming of interest in various disciplines of Earth and planetary sciences, including microbial ecology, biogeochemistry, geomicrobiology, and astrobiology. Microorganisms are often observed to colonize mineral surfaces, modify the reactivity of minerals either through the attachment of their own biomass or the glueing of mineral particles with their mucilaginous metabolites, and alter both the physical and chemical components of a geophysical system. Here, we hypothesise that microorganisms engineer their habitat, causing a substantial change to the information content embedded in geophysical measures (e.g., particle size and space-filling capacity). After proving this hypothesis, we introduce and test a systematic method that exploits this change in information content to detect microbial colonization in geophysical systems. Effectiveness and robustness of this method are tested using a mineral sediment suspension as a model geophysical system; tests are carried out against 105 experiments conducted with different suspension types (i.e., pure mineral and microbially-colonized) subject to different abiotic conditions, including various nutrient and mineral concentrations, and different background entropy production rates. Results reveal that this method can systematically detect microbial colonization with less than 10% error in geophysical systems with low-entropy background production rate.


Subject(s)
Bacteria/metabolism , Ecosystem , Entropy , Bacteria/growth & development , Biomass , Colony Count, Microbial
16.
Water Res ; 89: 76-86, 2016 Feb 01.
Article in English | MEDLINE | ID: mdl-26641013

ABSTRACT

An experimental study was conducted to test the hypothesis that the biomass growing after an increase in available nutrient in an aquatic ecosystem affects the flocculation dynamics of suspended particulate matter (SPM). The experiment was carried out in a settling column equipped with a turbulence generating system, a water quality monitoring system, and an automated µPIV system to acquire micro photographs of SPM. Three SPM types were tested combinatorially at five turbulence shear rates, three nutrient concentrations, and three mineral concentrations. Analyses of experimental data showed that nutrient availability together with the presence of biomass increased the SPM size by about 60% at low shear as compared to nutrient- and biomass-free conditions; a lower increase was observed at higher shears. In contrast, only 2% lower fractal (capacity) dimension and nearly invariant settling velocity were observed than in nutrient- and biomass-free conditions. Likewise, SPM size and capacity dimension were found to be insensitive to the SPM concentration. Although limited to nearly homogeneous mineral mixes (kaolinite), these experimental findings not only reject the hypothesis that SPM in natural waters can be dealt with as purely mineral systems in all instances, but also anticipate that SPM dynamics in natural waters increasingly exposed to the threat of anthropogenic nutrient discharge would lead to an increased advective flow of adsorbed chemicals and organic carbon.


Subject(s)
Biomass , Kaolin/chemistry , Nitrates/chemistry , Particle Size , Particulate Matter , Water Microbiology , Ecosystem , Flocculation , Water Pollutants, Chemical/chemistry
17.
Soft Matter ; 11(47): 9150-9, 2015 Dec 21.
Article in English | MEDLINE | ID: mdl-26414181

ABSTRACT

There has been growing interest in using the fractal dimension to study the hierarchical structures of soft materials after realising that fractality is an important property of natural and engineered materials. This work presents a method to quantify the internal architecture and the space-filling capacity of granular fractal aggregates by reconstructing the three-dimensional capacity dimension from their two-dimensional optical projections. Use is made of the light intensity of the two-dimensional aggregate images to describe the aggregate surface asperities (quantified by the perimeter-based fractal dimension) and the internal architecture (quantified by the capacity dimension) within a mathematical framework. This method was tested on control aggregates of diffusion-limited (DLA), cluster-cluster (CCA) and self-correlated (SCA) types, stereolithographically-fabricated aggregates, and experimentally-acquired natural sedimentary aggregates. Statistics of the reconstructed capacity dimension featured correlation coefficients R ≥ 98%, residuals NRMSE ≤ 10% and percent errors PE ≤ 4% as compared to controls, and improved earlier approaches by up to 50%.


Subject(s)
Models, Theoretical , Biocompatible Materials/chemistry , Diffusion , Optical Imaging
18.
Water Res ; 53: 180-90, 2014 Apr 15.
Article in English | MEDLINE | ID: mdl-24525067

ABSTRACT

An approach based on spheropolygons (i.e., the Minkowski sum of a polygon with N vertices and a disk with spheroradius r) is presented to describe the shape of kaolinite aggregates in water and to investigate interparticle collision dynamics. Spheropolygons generated against images of kaolinite aggregates achieved an error between 0.5% and 20% as compared to at least 32% of equivalent spheres. These spheropolygons were used to investigate the probability of collision (Pr[C]) and aggregation (Pr[A]) under the action of gravitational, viscous, contact (visco-elastic), electrostatic and van der Waals forces. In ortho-axial (i.e., frontal) collision, Pr[A] of equivalent spheres was always 1, however, stochastic analysis of collision among spheropolygons showed that Pr[A] decreased asymptotically with N increasing, and decreased further in peri-axial (i.e., tangential) collision. Trajectory analysis showed that not all collisions occurring within the attraction zone of the double layer resulted in aggregation, neither all those occurring outside it led to relative departure. Rather, the relative motion on surface asperities affected the intensity of contact and attractive forces to an extent to substantially control a collision outcome in either instances. Spheropolygons revealed therefore how external shape can influence particle aggregation, and suggested that this is equally important to contact and double layer forces in determining the probability of particle aggregation.


Subject(s)
Kaolin/chemistry , Models, Theoretical , Stochastic Processes , Water/chemistry , Flocculation , Hydrodynamics , Particle Size
19.
Rapid Commun Mass Spectrom ; 26(4): 430-42, 2012 Feb 29.
Article in English | MEDLINE | ID: mdl-22279019

ABSTRACT

RATIONALE: Earlier experiments demonstrated that isotopic effects during nitrification, denitrification and dissimilatory nitrate reduction can be affected by high (15) N contents. These findings call into question whether the reaction parameters (rate constants and Michaelis-Menten concentrations) are function of δ(15) N values, and if these can also lead to significant effects on the bulk reaction rate. METHODS: Five experiments at initial δ(15) N-NO(3) (-) values ranging from 0‰ to 1700‰ were carried out in a recent study using elemental analyser, gas chromatography, and mass spectrometry techniques coupled at various levels. These data were combined here with kinetic equations of isotopologue speciation and fractionation. Our approach specifically addressed the combinatorial nature of reactions involving labeled atoms and explicitly described substrate competition and time-dependent isotopic effects. RESULTS: With the method presented here, we determined with relatively high accuracy that the reaction rate constants increased linearly up to 270% and the Michaelis-Menten concentrations decreased linearly by about 30% over the tested δ(15) N-NO(3) (-) values. Because the parameters were found to depend on the (15) N enrichment level, we could determine that increasing δ(15) N-NO(3) (-) values caused a decrease in bulk nitrification, denitrification and dissimilatory nitrate reduction rates by 50% to 60%. CONCLUSIONS: We addressed a method that allowed us to quantify the effect of substrate isotopic enrichment on the reaction kinetics. Our results enable us to reject the assumption of constant reaction parameters. The implications of δ-dependent (variable) reaction parameters extend beyond the study-case analysed here to all instances in which high and variable isotopic enrichments occur.

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