OCN 401 Biogeochemical Systems

(Welcome!)

Instructors: Brian Glazer Kathleen Ruttenberg Frank Sansone Chris Measures

Textbook: Biogeochemistry, An analysis of Global Change by William H. Schlesinger & Emily S. Bernhardt Course Goals (SLOs)

1. Understand the underlying principles of biogeochemical cycling in aquatic and terrestrial Obj-1 systems.

2. Identify the major global pathways of bioactive elements and human perturbations of these pathways.

3. Develop / improve written and oral communication skills focused on biogeochemical processes. Obj-2

4. Achieve facility using electronic resources. Course Informational Resources

1. Syllabus with important due dates highlighted

2. Course Info Sheet – your ‘go to’ for ‘how to’

3. Professor Office Hours (by appointment)

4. Writing Assistance. - Manoa Writing Center - Course hand-outs - Meet with professors LECTURES Lectures will generally be given using PowerPoint presentations. As a convenience to students, copies of the PowerPoint slides will generally be handed out in class.

However, do not be fooled into thinking that the handouts are a substitute for careful note-taking in class. Much of the useful information in this class will be in the form of classroom discussion of the subject material.

Thus, students are expected to attend all lectures and to actively participate in class discussions.

GRADING Midterm Exam: 25%

Final Exam: 25%

Homework & Class Participation: 20%

Term Paper & Presentation: 30% The Text Book

Biogeochemistry, An analysis of Global Change by William H. Schlesinger & Emily S. Bernhardt

• Read chapter before class

• Subsections generally begin with an overview, and build from the general to the specific

• Almost without exception, very specific examples are given from the literature.

• Important to grasp the overview; understand but no need to memorize specific examples (with a few exceptions). Biogeochemical Systems (OCN 401) - Writing Intensive

In Class Peer Course Outline -- Fall 2016 Review

Lecture Day Date Topic Chapter Term Project Instr Homeworks #

Part I: Processes and Reactions Course Introduction. Discuss homework and term 1 Tu 23-Aug paper. Tree of life. 1, 2 BG Assign 1st mini-essay Metabolic pathways. Calculation of yields. 2 Th 25-Aug Atmospheric deposition, atmospheric models 3 CM 3 Tu 30-Aug Rock weathering and soil development 4 KCR 1st mini-essay due Return graded 1st mini-essay; Assign 2nd 4 Th and net 5 CM 1-Sep mini-essay 5 Tu 6-Sep Net primary production and global change 5 CM 6 Th 8-Sep Nutrient cycling in land plants 6 FS 2nd mini-essay due; Assign peer reviewers Peer reviews due; Discussion of Peer Reviewed mini-essays; Assign Discuss Peer review of 2nd mini-essay in Review of Electronic Library Research 7 Tu Extended Essay Topics; Review of Rubrics; Library - BG class; 13-Sep Methods research methods Assign Extended Essay Topics to students; BRIEF review of rubrics for Extended Essay 8 Th 15-Sep Nutrient cycling in land vegetation and soils 6 FS Cycling and biogeochemical transformations of N, P 1st draft Extended Essay due; Assign peer 9 Tu 6 FS 20-Sep and S reviewers mass balances and models of terrestrial 10 Th 22-Sep 6 FS nutrient cycling Discuss Term Paper Topic mini- Discuss peer review of essay drafts in 11 Tu Peer review of extended essays in class - presentation & Outline BG 27-Sep class; Draft revision plans in class Rubric Wetlands, and biogeochemical reactions in 12 Th 7 BG 29-Sep aquatic systems Wetlands, and biogeochemical redox reactions in 13 Tu 7 BG Final draft Extended Essay due 4-Oct aquatic systems 14 Th 6-Oct Lakes, primary production, budgets and cycling 8 KCR 15 Tu 11-Oct MID-TERM EXAM - ***Term Paper Topic Due beginning of class BG Return Graded Extended Essay ***Term Paper Topic mini-presentation 16 Th River transport and chemistry 8 BG 13-Oct *** (2 minute, 1 to 3 slide 17 Tu 18-Oct Estuarine and coastal ocean environments 8 BG *** Outline Due; Assign Peer Reviewers 18 Th Oceanic composition, circulation 9 KCR 20-Oct *** Oceanic production, carbon regeneration, nutrient 19 Tu 9 KCR 25-Oct cycling in the ocean - Part I Oceanic production, carbon regeneration, nutrient 20 Th 9 KCR 27-Oct cycling in the ocean - Part II ***Peer reviews due; Discuss Outline 21 Tu 1-Nov Peer Review Discussions 9 Peer Reviews in class; Draft revision BG plans in class ***

22 Th 3-Nov Hydrothermal vents 9 BG

23 Tu 8-Nov HOLIDAY - Election Day (no class)

Part II: Global Cycles 24 Th 10-Nov Oceanic sedimentary records 9 *** Final Outline Due *** BG 15-Nov The Global Carbon cycle - I 11 *** Outline Returned *** CM 17-Nov The Global Carbon cycle - II 11 CM 25 Tu 22-Nov The Global Phosphorus and Nitrogen cycles 12 KCR WED 23-Nov No class meeting, First Drafts due to BTG by end of day*** *** First Draft Due *** 26 Th 24-Nov HOLIDAY: Thanksgiving (no class) 27 Tu 29-Nov The Global and Mercury cycles 13 BG

Student Presentations -

28 Th 1-Dec Student Presentations-I (ALL) 29 Tu 6-Dec Student Presentations-II (ALL) 30 Th 8-Dec Student Presentations-III, course evaluations *** Final Draft Due *** (ALL)

12-Dec FINAL EXAM WEEK BG

Class: Tuesday & Thursday, 12:00 - 1:15 pm, MSB 307

Instructors: Brian Glazer, Chris Measures, Kathleen Ruttenberg, Frank Sansone Office Hours: 1:30-2:30 after lectures

Course Coordinator: Brian Glazer, MSB 226, x66658, [email protected]

Required Text: Biogeochemistry: An Analysis of Global Change, (3rd Edition) by W. H. Schelsinger and Emily S. Bernhardt

Final grade = Mid-term exam (25%); final exam (25%); class project (term paper, oral presentation) (30%); homework assignments and class participation (20%)

OCN 401 - Student Learning Outcomes: Upon successful completion of the course, students are expected to be able to: 1) Explain the underlying principles of biogeochemical cycling in aquatic and terrestrial systems. 2) Identify the major global pathways of bioactive elements, and the ways human activities affect these pathways. 3) Use written and oral communication to clearly explain biogeochemical phenomena and related contemporary research. 4) Achieve facility using electronic resources (e.g. on-line journals, electronic searches for science references) to develop a bibliography for a research area.

BTG Page 1 8/23/16 Homework

i) Mini-essays (2) writing mechanics (2-3 pp) ii) Extended essay critically review literature on a technical subject, organize arguments (3-5 pp)

Term paper and presentation synthesize skill sets emphasized in homework categories (i) and (ii) Term Project

Products: – Term paper (70% of term project grade) – Oral presentation (30% of term project grade)

Component parts of project: – Choose a topic (must get instructor’s approval!) – Mini-presentation of topic (1 to 2 slides / 2 minutes) – Detailed, annotated outline for term paper; peer review – Submit a complete draft of your term paper for instructor comments – Submit corrected final draft of term paper – In-class oral presentation of paper with peer review Term Project Due Dates

Due dates are FIRM. Late assignments will be docked points (10% per day). See me in advance if you are unable to meet deadlines to arrange extension. Extensions will be granted only for emergency situations.

Date Assignment 10/11 Term project topic due 10/13 Mini-presentations of topics 10/20 Outline due 11/1 Outline peer reviews due 11/10 Final Outline due WED - 11/23 1st draft of paper due 11/29 1st draft returned 12/1 Oral presentations Meet with KCR to discuss paper revisions 12/6 Oral presentations 12/8 Oral presentations 12/8 Final paper due Past Term Paper Topics

(Note: These examples cannot be used this year)

2015 • Soil organic carbon and tillage • Ice algae and climate change • Glacial-interglacial variations • Sulphur dioxide emissions in China: the acid rain issue and abatement solutions •How diatoms influence the biogeochemistry of the Sargasso •Allocthonous fluxes of iron to the ocean •The role of biogeochemistry on color formation in Champagne Pool, NZ •Storm runoff influence on nutrient and phytoplankton dynamics in Kaneohe Bay •How Lake Constance total suspended matter is affected by spring alpine snowmelt Past Term Paper Topics

(Note: These examples cannot be used this year)

2015 (cont) • Past & present methane production from Holocene wetlands as an indicator of spatial and temporal methane under a future climate regime •Invasive plants in Hawaii: impacts on nutrient cycling •Global carbon fluxes to the coastal ocean •Effects of climate change on carbon accumulation in peatlands Past Term Paper Topics

(Note: These examples cannot be used this year)

2014 • El niño southern oscillation and subsequent effects on weathering and nutrient distributions along the eastern pacific • Effects of anthropogenically induced change on salt marsh in california • Acid rain: effects on lake and terrestrial ecosystems • Sedimentation on coral reefs: A comparison of reefs in the hawaiian islands and puerto rico • An analysis of the physical and biogeochemical impacts of heinrich events • Influence of jellyfish blooms on nutrient cycles • Redox regime of biogeochemical successions in he’eia fishpond • Future changes in oceanic dissolved oxygen concentrations Past Term Paper Topics

(Note: These examples cannot be used this year)

2014 (cont’d)

•High Temperature Geothermal Sources of Hawaii and New Zealand: Water Chemistry and Associated Microbial Communities •Picoplankton Photoheterotrophic Production in the Subtropical North Pacific Ocean •Methane Hydrates: Formation, Distribution and Potential Effects on Climate •The Effects of Urban Runoff on Coral Communities Past Term Paper Topics

2013 • Biochar Addition and Greenhouse Gas Emissions from Soil • The Sulfur Cycle in Marine Environments • Oceanic anoxic events of the Cretaceous Period Methane formation and oxidation in continental margin sediments • Impacts of Land Use on Coastal pH • Contrasting the Impact of Ocean Acidification on Coral Reef Organisms vs. Sea Anemones • The Roles of Macro-scale, Meso-Scale, and Micro-scale fauna and flora in soil formation and carbon cycling

• How Did Coral Reefs Affect CO2 Levels During Deglaciation? • Paleoclimate Reconstruction with Coccolith Vital Effects Past Term Paper Topics

2012 • Increase in nutrient loads and how that affects corals • in the marine environment • Biochar, a way to improve soil quality and plant • Methane formation and oxidation in continental margin sediments

• Increasing CO2 and the affect on trees • Changes in calcification rates of marine invertebrates in response to increased

atmospheric CO2 • Urban runoff effects on microbial communities in receiving bodies • Physical enrichment of nutrient uptake in corals • How the hydrological cycle of wetlands affects the release of greenhouse gases • Tracer transport in oceanic crust on the Juan de Fuca Ridge 2012 (cont’d.) • Consequences of carbon enrichment on nitrogen biogeochemistry in subtropical oceans • Carbon budgets in estuaries • From Mississippi to the Gulf of Mexico: Runoff, leaching and the dead zone • Origination of sequestered carbon in northern cryosphere and potential releases • Anthropogenic influences on silicate weathering rates in river basins and the implications for atmospheric CO2 concentrations • Environmental impacts of a geothermal power plant • Soil development in the North American Prairies in the last 100 years • Precambrian stromatolite formations: Biogeochemical processes of early archaic life forms •Carbon cycle in coastal upwelling regions •The biochemical effects on chalcopyrite leaching •Diapycnal and isopycnal mixing 2011 • Arctic sea ice: Adaptations and ecological ramifications. • Delivery of anthropogenic nitrogen to the coastal ecosystem on basaltic shorelines by submarine groundwater discharge. • Biochar double whammy: Carbon sequestration and increased food production. • Methane formation and oxidation in continental margin sediments. • Sediment redox chemistry in mangrove forests: He’eia Fishpond as a case study. • Soil acidity and agricultural productivity of oxisols and ultisols in the tropics. 2010

• Environmental and biogeochemical changes associated with the evolution of eukaryotes. • Spatial and temporal variability of the biogeochemical response to storm runoff in southern Kaneohe Bay, Oahu, Hawai’i. • Lake Kivu: Catastrophe or gift of energy? • Methane hydrates: Formation, stability, and effects on global climate.

• Effects on coral growth due to increased atmospheric CO2. • Mercury methylation in the marine environment. • The effects of ocean acidification on the benthos. • The generation, migration and climatic effects of coastal methane seeps. • Oxygen minimum zones: Understanding the global biogeochemical characteristics of OMZs. • The formation of biogenically derived marine aerosols, air-sea transport, and ecological effects. • Factors influencing organic carbon sequestration in marine environments. • The role of submarine groundwater discharge in coastal nutrient dynamics. • Dammed nations, or damned ocean? The effect of dams on the coastal zone.

• Carbon capture and sequestration: Deep-sea CO2 injection. 2009 • Agricultural soil erosion: Carbon sink or source? • Beachrock: Evidence of shoreline change. • of toxic metals in fresh water and coastal marine systems: Arsenic, mercury and lead. • Effect of agriculture on nutrient loading in the Mississippi River: The Gulf of Mexico Dead Zone. • Forest fires and nutrient cycling. • New hypoxic zone: A comparison with other dead zones and implications of ocean current changes in the northwest Pacific Ocean. • Nutrient cycling within subsurface chlorophyll maximum and plankton thin layers. • Carbon sequestration: A comparison between biological and geological approaches. • Air pollution and atmospheric deposition in Istanbul. • Nitrogen fixation in the North Pacific Ocean. • Effects of submarine groundwater discharge on nutrient cycling and ecosystems. 2008 • Sediment transport in coastal areas • As cycling in marine environments • Nutrient supply in Pacific versus Atlantic eddies • Biogeochemical interactions between the benthos & sediments

• CO2 sequestration in deep sea, acidification effects • Estuarine & denitrification • Nutrient uptake ratios & phytoplankton selection • Biogeochemical changes during PETM • Environmental causes of ciguatera outbreaks • Role of nutrients in HABs

• CH4 production in natural systems • Eutrophication: causes & oyster remediation • Anoxic conditions related to nutrient input Exams

There will be a 75-minute mid-term exam on October 11 and a 2-hour final exam on December 15. The final exam will cover all of the semester’s course material. Exams will cover the readings, lectures, and topics discussed in class.

Exams will be open book. Please bring a calculator.

Copies of previous exams can be examined in the Oceanography Office (MSB 205); these can give you an idea of the types of questions to be expected. However, it is very unlikely that any exam questions will be repeated!

No absences are allowed from any exam, except under circumstances totally beyond your control. Except for medical emergencies, excuses must be submitted and approved before the day of the exam. Mini-Essay #1 Assignment Sheet

Overview of assignment:

Read the assigned article: Marine carbon sinking rates confirm importance of polar oceans (Science Daily, 07/25/16), and write a 2 to 3 page Mini-Essay on some aspect of the article. The objective of this writing assignment is to employ excellent writing mechanics and style, and to compose a brief, easily readable essay.

Assignment Due Date: August 30 (Tuesday)

Instructions:

1.Read over the Mini-Essay writing rubric to familiarize yourself with the criteria that will be used to evaluate the essay. 2.Read over the Mini-Essay grading template to see how points will be distributed among the different assessment criteria. 3.Read the assigned article and compose a mini-essay on some aspect of the article. The essay need not be a strict summary of the article – feel free to take literary license, as long as your essay is well written. 4.You must use 11 pt (PC) or 12 pt (Mac) font. 5.Text must be double-spaced. 6.You must number the pages. 7.Give your essay a title, and put your name, the date, the assignment type and the course # in the header. 8.You must underline the topic sentence of EACH paragraph! 9.You must not exceed the page limit!

See handout: Paragraphs & Topic Sentences Writing Rubric for Mini-Essays Mini-Essay Grading Template GES Capstone Course: Global Cycles and Underlying Processes

• Utilize the knowledge base you have built over the past semesters as a GES student

• Apply this knowledge to the understanding of biogeochemical processes in different Earth environments

• End with synthesizing into an overview of global cycles of elements, emphasizing processes and coupled cycles

• Venture into discussions of extrapolating knowledge of current Earth biogeochemical cycles to the Earth’s past and future

The “Tree of Life” Metabolic Pathways Calculation Of Energy Yields

OCN 401 - Biogeochemical Systems 8/23/16

Reading: Schlesinger & Bernhardt, Chapters 1 & 2

some slides borrowed from Frank Sansone Outline

1. Earth’s history and the evolution of life

2. The “Tree(s) of Life”

3. Metabolic strategies by organisms

4. Linkages between reductions and oxidations (redox)

5. Calculation of energy yields How does the Earth work as a biosphere?

Where did we come from? -origin of life questions

Are we alone? -how does Earth “work” -what kind of disequlibria do we look for in distant atmospheres? From David Darling Sustaining life on a planet

All organisms derive energy for growth and maintenance by moving electrons from a substrate to a product

All substrates and products must ultimately be cycled

Biological processes are paired e.g., photosynthesis and respiration

All metabolic processes on Earth are prokaryotic and were derived in the Archean and/or Proterozoic Eons Some perspective

• The history of life on earth is overwhelmingly microbial • The earth is ~4.5 billion yrs old, – microbes arose 3.8 billion years ago (bya) – animals-0.7 bya -- humans-0.001 bya Jan. 1-Earth Forms The Microbial Age-3.1 Billion Years

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Late Feb-Microbes ~Nov. 5th-Animals (oceans)

Dec. 11th-Land Plants

Dec. 27th-Mammals

Dec. 31st-10:00 PM Humans 11:59:30 PM Written History Chemistry of life centers on the disequlibrium redox chemistry of “the big six”

H, C, N, O, P, S Primary role of P is in forming phosphates, binding to C, forming organics, whereas other 5 facilitate electron transfer GER

…and at least 54 other “trace elements” (Fe) How did CHON monomers arise on early Earth? • Oparin (1924) – Life is simple àcomplex

– No “plants” à no O2 – Early organics from space à accumulate • Organic “broth” in sea • Stanley Miller (1951)

– H2, N2, CO2, H2O, NH3, CH4 – Reducing atm + UV or lightening à organics – Produced amino acids The Miller-Urey experiment: Abiotic synthesis of organics

• Simulated early Earth – Reducing atmosphere

• H2O, H2, CH4, NH3 – Simple inorganic molecules – Electric sparks (lightning) • Produced amino acids and other organic molecules • Couldn’t happen under modern conditions – Oxidizing atmosphere attacks organic bonds • Or: possibly Earth was contaminated with organics from space Earth, ~3.5 bya • Shallow sea environment – Land covered by low egg- shaped hills, diameter 20- 50 km Pillow lava – Silt layers – Scattered volcanic islands à evaporite lagoons • Tides higher – Moon closer to Earth, days shorter • Atmosphere

– CO2-rich, no O2 – UV-drenched landscape Evidence for the timing of the origin of life on Earth • Fractionated carbon isotopes at 3.8 Ga (Isua Fm., Greenland) • Filaments of cyanobacteria (blue-green algae) in 3.4 Ga cherts (in western Australia, South Africa) • Stromatolites at 3.3-3.5 Ga (Warrawoona Group, Australia)

• Anaerobic: evolved outside the presence of free oxygen (free oxygen would probably poison it!) • Heterotrophic: a , absorbing molecules from water • “Prokaryotic”: no nucleus nor other complex organelles A Modern Approach

Determined from sequencing of ribosomal RNA (as opposed to morphology and physiology)

Bacteria Eucaryotes

Euryarchaeota

Cren- archaeota

“Last universal common ancestor”

Archaea – most “primitive”, commonly live in extreme environments Modified from Chan et al. (1997) A further complication – endosymbiosis, lateral gene transfer, etc. The New Paradigm??

Swithers & Katz 2013 Metabolic Strategies for Sustaining Life

We can classify organisms by function -- how they obtain energy and cell-carbon: 1. Method of energy generation (reactions that convert ADP to ATP): • Photosynthesis --

e.g.: Oxic photosynthesis: 6 CO2 + 6 H2O ® C6H12O6 + 6 O2 + ATP • Oxidation/reduction of inorganic compounds -- (Chemotroph)

+ - + e.g.: oxidation: NH4 + 1½ O2 ® NO2 + 2 H + H2O + ATP • Oxidation of organic compounds --

e.g.: Glucose oxidation: C6H12O6 + 6 O2 ® 6 CO2 + 6 H2O + ATP 2. Carbon source: • Carbon dioxide -- • Organic compounds -- Metabolic Strategies - Examples

Photoautotrophs Green plants Most algae Cyanobacteria Some purple and green (Autolithotrophs)

+ - Methane oxidizing bacteria: CH4 + O2 ® CO2 + 4H + 4e oxidizing bacteria Iron oxidizing bacteria

- - Nitrifying bacteria: NO2 + ½ O2 ® NO3 Most purple and green non-sulfur bacteria Some algae Some cyanobacteria Lithoheterotrophs (Heterolithotrophs) Sulfide oxidizing bacteria Organoheterotrophs Animals Most bacteria Fungi Protozoa Linkages Between Oxidations and Reductions

Oxidized Reduced

2 Oxygenic O Photo- ® synthesis O CH2O º 2 H

generic CO2 ® CH2O organic

Aerobic Denitrification 2 Anaerobic 2 Respiration respiration CO matter CO ® 2 ® ® O 2 O Oxidized CO O 2 2 CH CH

CH NO3 ® N2 O2 ® H2O SO4 ® H2S

Chemo- 3 autotrophic

These are the NO nitrification ® most common 4 NH redox CO2 ® CH2O

reactions; Reduced

4 Chemo- autotrophic many others SO sulfur oxid ®

are possible S 2 H CO2 ® CH2O

In this course we will see that global biogeochemical cycles are driven by transformations of substances between oxidized and reduced forms in different environments Calculation of Energy Yields

Consider this general reaction: aA + bB ® cC + dD

The free-energy change of the reaction at “standard state” can be calculated as:

Gr ° = (cGC ° + dGD °) - (aGA° + bGB °)

where GX° is the free energy of formation for a product or reactant “X” at standard state (which can be looked up)

Standard state: 1 atm pressure 25°C Concentrations = 1 mole/kg • If DGr° < 0, then the reaction proceeds spontaneously as written (at standard state)

• If DGr° > 0, then the reaction proceeds spontaneously in the opposite direction as written (at standard state)

• If DGr° = 0, then the reaction is at equilibrium and will not proceeds spontaneously in either direction (at standard state)

Thus, DGr° is a powerful tool to predict if a reaction will occur!

However, we are commonly interested in conditions other than standard state.... We calculate the in-situ DGr using this equation:

[C] c [D]d G = G ° + RT ln r r [A] a [B]b In-situ Standard state R = ideal gas constant = 1.987 cal °K-1 mol-1 = 8.31 J °K-1 mol-1 T = °K [ ] = concentration

Thus, using the same criteria used on the previous slide, we can predict whether a reaction will occur under real-world conditions! (we’ll do more of this later in the course, but good to review) The next lecture: “Atmospheric deposition, atmospheric models”

This will begin our investigation of biogeochemical systems on Earth: • Atmosphere • Terrestrial systems • Aquatic systems • Lakes • Streams and rivers • Estuaries • Oceans