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Institute of Food and Agricultural Sciences (IFAS) Biogeochemistry of Wetlands Science and Applications Biogeochemical Indicators Wetland Biogeochemistry Laboratory Soil and Water Science Department University of Florida Instructor K. Ramesh Reddy [email protected] 7/17/2015 7/17/2015 WBL 1 1 Biogeochemical Indicators Topic Outline 7/17/2015 Introduction Concept of indicators Guidelines for Indicator Development Levels of Indicators Sampling protocol an design Data analysis WBL 2 Biogeochemical IndicatorsNutrient Impacts/Recovery What physical, chemical, and biological properties are affected by nutrient impacts? What biogeochemical processes are affected by nutrient loading to wetlands? What biogeochemical indicators or endpoints can be measured to determine nutrient impacts/recovery of wetlands? Is there a sufficient range of values for biogeochemical indicators so that they may serve as sensitive indicators of nutrient impact/recovery? Does the distribution and central tendency of biogeochemical indicators discriminate between natural spatial variability and anthropogenic impact in wetlands? 7/17/2015 WBL 3 Guidelines for Indicator Development Conceptual Relevance: Is the indicator relevant to the assessment question (management concern) and to the ecological resource or function at risk? Feasibility of Implementation: Are the methods for sampling and measuring the environmental variables technically feasible, appropriate, and efficient for use in a monitoring program? Response Variability: Are human errors of measurements and natural variability over time and space sufficiently understood and documented? Interpretation and Utility: Will the indicator convey information on ecological conditions that is meaningful to environmental decision-making? (Jackson et al., 2000, USEPA). 7/17/2015 WBL 4 Nutrient Cycling in Soil and Water Column Emergent macrophyte Submerged macrophyte Periphyton Water Soil N C P Bioavailable nutrients S 7/17/2015 WBL 5 Nutrient Impacts on Detritus, Soil, and Water Impacted Hours to Days < 2 years Unimpacted Water Detritus Hours to Days < 2 years < 50-100 years < 10-15 years >10- 15 years 7/17/2015 0-10 cm > 50-100 years 10-30 cm WBL 6 Nutrient Impacts in Wetlands External Nutrient Load Periphyton Vegetation Water Internal Nutrient Load Detritus 0-10 cm 10-30 cm 7/17/2015 Microbial/Chemical Processes WBL 7 Response Time Cost Sensitivity Spatial Resolution Biogeochemical Indicators Micro Macro Scale of measurement of a Process or an Indicator, and it’s influence on cost and response time 7/17/2015 WBL 8 Biogeochemical Processes/Indicators Nutrient load Hydrology Sediment load Soil-Water Column Spatial/ Temporal Patterns Biogeochemical Process Stressors/ Regulators Biogeochemical Indicator [Endpoint] Ecological Function Algae/ Vegetation 7/17/2015 Fish Diversity WBL Microbial Diversity 9 Biogeochemical Indicators The indicators can be measured at three levels: Level I - low cost, easily measurable, and less sensitive. Level II - medium cost, moderate complexity, and moderately sensitive. Level III - high cost, very complex, and highly sensitive. 7/17/2015 WBL 10 Biogeochemical Indicators Level I - Indicators Water column: Causal variable Detritus/Soil: Response and Causal variables Level II – Indicators Water, detritus, and Soil: Response variables Level III – Indicators Water, detritus, and Soil: Response variables 7/17/2015 WBL 11 Level - I Water Column • Dissolved oxygen • Bioavailable nutrients • Ammonium N; nitrate N; dissolved reactive P; dissolved total P • • • • • 7/17/2015 Total phosphorus and nitrogen Chemical composition of periphyton Total organic carbon and dissolved organic carbon Carbon-nitrogen ratios Carbon-phosphorus ratio • • • • • • • • • • • WBL pH Suspended solids Conductivity Salinity Turbidity Alkalinity Color Biochemical oxygen demand Water depth Hardness Conservative tracers 12 Level - I 7/17/2015 Soil and Detrital/floc Layers Floc depth Bulk density Soil pH Soil redox potential Extractable nutrients (HCl and Mehlich III) Extractable ammonium Loss on ignition (LOI) Total P, N, and S C:N:P:S ratios Extractable metals WBL 13 Level - II Water Column • Primary productivity • Heterotrophic respiration • Extracellular enzyme activity • Species composition of periphyton • Diel pH and dissolved oxygen • Biological nitrogen fixation 7/17/2015 WBL 14 Level - II 7/17/2015 Soil and Detrital/floc Layers Microbial biomass C,N,P, and S Enzyme activities Soil porewater nutrients Soil phosphorus forms Organic nitrogen Organic and inorganic sulfur Single point phosphate isotherm Extractable metals Total mercury Pesticides Soil mineralogical composition WBL 15 Level - II Soil and Detrital/floc Layers Soil oxygen demand Soil-water nutrient exchange rates Organic matter accretion rates Equilibrium P concentration (EPCo) Phosphorus partition coefficients Detrital decomposition rates Potentially mineralizable P, N, and S Nitrification, and denitrification Iron and sulfate reduction Methyl mercury Methanogenesis Microbial respiration 7/17/2015 WBL 16 Level - III Water Column • Microbial diversity • Cellular fatty acids • rRNA sequence analysis 7/17/2015 WBL 17 Level - III Soil and detrital layer • Substrate Induced: • Microbial respiration • Organic nitrogen mineralization • Organic phosphorus mineralization • Microbial diversity • Cellular fatty acids • rRNA sequence analysis • Phosphate sorption isotherms • Equilibrium phosphorus concentration (EPCo) • Phosphorus sorption coefficients • Mineralogical composition • Stability of phosphate precipitates and minerals • Stable isotopes • Organic P and C characterization (NMR) 7/17/2015 WBL 18 Level - I Response Variable Linkage between Level – I Indicators and Nutrient Load Nutrient Load 7/17/2015 Causal Variable WBL 19 Level - II Response Variable Linkage between Level – I and Level – II Indicators Level - I 7/17/2015 Causal Variable WBL 20 Level - III Response Variable Linkage between Level – II and Level – III Indicators Level - II Causal Variable 7/17/2015 WBL 21 Data Analysis Primary Data Monitor Indicators STA Performance Evaluation Level I Analyze Data Identify Indicators Level II Model Parameters 7/17/2015 WBL Hydro-Biogeochemical/ Statistical Models 22 Indicator Evaluation ? Complementary Indicators Ratio of impacted site relative to reference site Comparison of sensitivity, time and effort 7/17/2015 WBL 23 Nutrient Impact Index Impact Index: log [IS/RS] 2 1 Impacted Site [IS] Reference Site [RS] 0 Background level -1 -2 Distance from inflow 7/17/2015 WBL 24 1 Impact Index Impact Index: log [IS/RS] Severe impact 0.5 Moderate impact 0 No Impact- background condition Moderate impact -0.5 Severe impact -1 7/17/2015 WBL 25 Total Phosphorus in WCA-2A soils (0-10 cm) 1990 7/17/2015 1998 WBL 26 Extracellular Enzymes [Water Conservation Area-2A] Impact Index = log [IS/RS] Enzymes Detrital layer B-D-Glucosidase Protease Alkaline Phosphatase Arylsulfatase Phenol Oxidase 7/17/2015 WBL 0.56 0.16 -0.70 -0.10 0.19 Soil 0-10 cm] 0.40 0.07 -0.37 -0.12 0.16 27 Organic Matter Decomposition [Water Conservation Area-2A] Impact Index = log [IS/RS] Process/ Indicator Detrital layer Respiration Aerobic Anaerobic 0.21 0.41 0.23 0.28 0.33 0.30 0.11 0.15 MBC MBC/TOC Soil [0-10 cm] MBC = Microbial biomass carbon 7/17/2015 WBL 28 Nitrogen Transformations [Water Conservation Area-2A] Impact Index = log [IS/RS] 7/17/2015 Process/ Indicator Detrital layer Soil [0-10 cm] PMN SINM (Alanine) MBN SINM/MBN Nitrification Denitrification N2 fixation 0.40 0.62 0.23 0.39 0.17 0.31 1.0 0.25 0.45 0.12 0.33 0.20 0.31 SINM = Substrate induced nitrogen mineralization WBL MBN = Microbial biomass nitrogen 29 Phosphorus Transformations [Site: WCA-2A] Impact Index = log [IS/RS] 7/17/2015 Process/ Indicator Detrital layer PMP SIPM (G-6-P) MBP SIPM/MBP C/P ratio Labile Pi 0.85 0.08 0.33 -0.28 -0.51 1.07 Soil [0-10 cm] -0.03 -0.41 0.17 -0.48 -0.51 0.52 PMP = Potentially mineralizable P; SIPM = substrate induced P mineralization MBP = microbial biomass P WBL 30 Microbial Biomass N and PMN Floc- Total N and P Ratios 200 MBN 4000 PMN (mg kg-1 d-1) MBN (mg kg-1) 5000 3000 2000 1000 0 0 7/17/2015 100 200 300 Molar N:P ratio 400 PMN 150 100 50 0 0 100 200 300 400 Molar N:P ratio WBL 31 Microbial Biomass P and PMP Floc- Total N and P Ratios 500 30 MBP (mg kg-1) PMP (mg kg-1 d-1) MBP 400 300 200 100 PMP 20 10 0 0 0 7/17/2015 100 200 300 Molar N:P ratio 400 WBL 0 100 200 300 Molar N:P ratio 400 32 Impact Index – Detritus/Floc- WCA-2a 1 Microbial Populations [ 1.7 -2.1] N2 fixation, PMP, Labile Pi High impact Impact Index: log [IS/RS] B-D-Glucosidase 0.5 Microbial Respiration, MBC, MBP, PMN, SINM, TP, and TPi Moderate impact Protease, MBN, Phenol Oxidase, nitrification, Denitrification 0 Arylsulfatase, TC, TN No Impact- background condition Moderate impact -0.5 Alkaline Phosphatase Activity, C/P ratio, N/P Ratio High impact -1 7/17/2015 WBL 33 Data Analysis and Synthesis Descriptive statistics to define frequency distribution and central tendency of biogeochemical indicators Multivariate analyses to evaluate relationships between biogeochemical indicators and ecological condition Geostatistical analyses to evaluate spatial patterns and spatial structure of biogeochemical indicators Predictive modeling to forecast evolution of biogeochemical indicators and ecological integrity 7/17/2015 WBL 34 Stepwise Canonical Discriminant Analysis: Abiotic Indicators: Everglades –WCA-2a Canonicla Variate 1 (u1) 10 8 Site F1 F4 U3 6 4 2 0 -2 -4 -6 -4 -3 -2 -1 0 1 2 3 4 5 Canonical Variate 2 (u2) 7/17/2015 WBL 35 Stepwise Canonical Discriminant Analysis: Biotic Indicators: Everglades –WCA-2a Canonical Variate 1 (u1) 4 Site 3 F1 F4 U3 2 1 0 -1 -2 -3 -4 -3 -2 -1 0 1 2 3 4 5 Canonical Variate 2 (u2) 7/17/2015 WBL 36 Biogeochemical Indicators Paradigm Key Challenges Simultaneous measurements of “processes” and ‘indicators” at various spatial and temporal scales Integration of these measurements across scales using statistical and process models 7/17/2015 WBL 37 Minimum Data – Level I Water column: Water depth Total Nitrogen Total Phosphorus 00- cm Detritus/Floc: Total carbon, Total nitrogen Total phosphorus 0- cm Detrital Floc Soil: 7/17/2015 Bulk density Organic matter content, Total carbon, Total nitrogen, Total phosphorus, Extractable nitrogen, Extractable phosphorus (Mehlich –1 and 3) Extractable Fe, Al, Ca, Mg, and K WBL Soil 10 cm 38 Soil Sampling in 2003 Stratified random sampling design Total number of sampling sites (n): 1,349 (+~10% replicates) Floc/detritus 0-10 cm 7/17/2015 10-20 cm WBL 39 Biogeochemical Indicators Summary Indicators may reflect biological, chemical, or physical attributes that can be used to characterize current status or to predict impact or change. Such indicators of wetland ecosystem integrity should be sensitive, reliable, accurate, rapid, and inexpensive. Indicators should be clearly understood and accepted by scientists, environmental managers, and policy makers. Indicator levels in accessing impact to wetland ecosystem may be based on the ease of measurement and the ability to respond to change. Level I indicators are easily measurable whereas level II and III indicators provide more scientifi c rigor and are used to support easily measurable indicators 7/17/2015 WBL 40 Biogeochemical Indicators Summary Wetland can exhibit a high degree of spatial heterogeneity; thus, the sampling protocol should aim to capture the underlying spatial variability of wetland indicators. The selection of indicator variable, sampling design, data collection, and statistical/geostatistical methods to analyze dataset is linked. Before using any selected biogeochemical indicator, a sampling design must be established that represents unimpacted and impacted portions of the wetland to assess early warning signals of decline in ecosystem health. Each sampling protocol, if possible, should compare environmental conditions to a reference or control site. 7/17/2015 WBL 41