Nitrogen levels in the Piracicaba River in So Paolo, Brazil

Andrea Maria Fernandez Smithers Key words: nitrogen, BPWN, Piracicaba, sugarcane

Fernandez Smithers 2 Project Summary: This proposal will detail a study to sample water discharging into the Piracicaba river basin, focusing on areas of the basin that come into closest contact with sugar cane plantations. The target area of interest for this study is located in the state of So Paulo in southeast Brazil, although the river originates in the state of Minas Gerais. Water sampling would occur for a full period of 2 years to allow sufficient time to account for expected rise and fall of these nitrogen levels in times of wet and dry season, maturing and harvesting season, and burning of the sugar cane fields, as well as to account for the full maturing period of some longer-growing plantations. During the sampling process, partnership work will be done with the Universidade Metodista de Piracicaba (UNIMEP) to provide opportunity for students there to do joint research, as well as to cut down on traveling and shipping costs. The university is equipped with necessary Nitrogen testing equipment and is extremely close to all sampling sites, providing for better accuracy of the tests because of shorter holding times. Remediation recommendation is to implement Baojing Gus method of biofuel production using waste Nitrogen (PBWN). Water Nitrogen samples would provide a basis for analysis of potential impact of PBWN, and a savings-benefit plan could be developed for the four plantations. Using simple contour elevation software (such as autoDEM or an equivalent), a wastewater and Nitrogen waste water distribution system can be designed to water and fertilize more sugar cane plantation land. Some of this would be done simultaneously to sampling. The potential impact for this project is a huge reduction in anthropogenic reactive Nitrogen disposal into the Piracicaba River basin, thus reducing already-seen eutrophication in the area, and impacting the Piracicaba River and the large Tiet and Paran Rivers that it feeds, which sustain more than 20 million people in southeast Brazil. This project would also cut costs for the sugar cane plantations and there is probable expansion to other plantations in the area.

Fernandez Smithers 3 Project description A. Nature, Scope, and Objectives As the worlds population increases and the demand for energy soars, energy alternatives to oil, gas, and coal are on the rise. In 2010 alone, Brazil used 348 metric tons of sugarcane to produce ethanol (Heffer 2011). This number is on the rise annually and this drives the increased use of fertilizer. In 2008, Brazils consumption of fertilizer by sugarcane was 2.9 million tons, and every year there is a 2-3% increase in these figures (Allen, et al). This is a significant concern when considering that eutrophication effects from excess anthropogenic nutrient discharge have already been seen for years in the Piracicaba River basin, and in turn, in the water quality of the large rivers it feeds in the state of So Paulo. Sustainable remediation efforts are no longer a dream option, but a pressing need. The main objectives of this project are to aid in the reduction of anthropogenic reactive Nitrogen discharge into the Piracicaba River Basin from over fertilization of sugar cane in numerous sugar cane plantations and to develop a Biofuel Production Using Waste Nitrogen (BPWN) design. The project will focus on only four plantations, determined based on closest direct geographical location to the basin, as to better differentiate watershed from the plantations and from other industrial and/or household wastewater. Water samples will be tested for total reactive Nitrogen and this information will then be used to develop a plan for implementing BPWN. This analysis will include developing methods to better quantify the BPWN potential and impact for an area, which will be useful in the expansion of BPWN utilization in other plantations in the basin areas. The study will not look at other fertilizer nutrients like Phosphorus and Potassium, nor will it test for metallic contaminants. The BPWN design will not include extensive mathematical modeling; rather, it will be attained mostly through fluid dynamics planning using the data gathered from simple elevation information available through GIS. This project does not have hopes of remediating the total reactive Nitrogen in the basin as pertains to industrial, domestic, and other fertilized crops (outside of the four targeted plantations), but hopes to provide a foundational starting point to reduce the total level by practically eliminating these four plantation nitrogen discharges, and catapult the potential expansion into other sugarcane plantations and even other crops in the future, not necessarily tied to the project this proposal is outlining.

Fernandez Smithers 4 B. Literature Review Having high levels of Nitrogen in the water system is an ecological problem that has been building for years world-wide. Some of the major and most frightening known effects from high concentrations of Nitrogen include: Eutrophication Dead Zones Blue baby syndrome

The high nutrient levels in discharge water coming into rivers, lakes, and oceans provoke excess growth of microscopic plants, algae, and floating plants in the water. This causes the eco system to be depleted of oxygen very quickly because these plants utilize the oxygen as well as preventing aeration in the system because of the barrier they tend to form on the top layer of the water body. When the plants die and sink to the bottom, microorganisms then decompose the residue using up enormous amounts of oxygen. Complete deoxygenation , or anoxia, can quickly present itself as a reality in these nutrient-high systems. These conditions are not suitable for fish and other riverine or marine fauna and they eventually either flee or die. When the level is so anoxic that sediment and water begin to lose oxygen, the levels released of ammonia and hydrogen sulfide can even be toxic to plants and animals near the water body (Water Quality: The Impact of Eutrophication). Dead zones are an extreme and long-term effect of eutrophication. These oxygen depleted areas from layers in the ocean bottoms across the globe allow no living creature to inhibit in their anoxic conditions. The number of dead zones in the world has doubled every decade since the 1960s, and in 2006, over 200 dead zones were reported world-wide (Schrope, 2006). These dead zones are catastrophic not only for the water-dwelling creatures, but also for humans. Economically, coastal areas in every country depend on fish, lobster, crab, and more for living. Infant Methemoglobinemia, also known as the blue baby syndrome, is a condition most commonly linked to Nitrate-contaminated drinking water, although some high-concentration Nitrate foods have also been linked as culprits. Infants under 6 months of age are extremely susceptible to this condition because of their low levels of methemoglobin reductase, although

Fernandez Smithers 5 drug reactions, some chemical exposure, and rare hereditary deficiencies can also increase methemoglobinemia risk. Affected persons develop a blue-gray hue in their skin and can have low-energy symptoms. If the condition is not identified and treated quickly, however, suffering persons can quickly see coma or death (Knobeloch, et al., 2000). This is a particular problem because of Brails extremely high density population. The Piracicaba River is a tributary of the Tiet River, which is a tributary of the Paran. This is a huge population, starting with the fact that the Tiet runs down the center of the city of So Paulo, one of the largest cities in the world, and this river is one of its primary water sources. Below is the susceptible population, showing all children under 10 years of age in 2010 for Southeast and South Brazil.
Pessoas de at 10 anos de idade Grandes Regies e Unidades da Federao Brasil Sudeste Minas Gerais Esprito Santo Rio de Janeiro So Paulo Sul Paran Santa Catarina Rio Grande do Sul Grupos de idade Total Menos de 1 ano 32 270 750 12 175 001 3 044 050 570 889 2 349 755 6 210 307 4 155 574 1 664 766 946 208 1 544 600 2 713 244 1 026 440 249 075 48 994 195 200 533 171 354 173 144 631 81 608 127 934 1 ano 2 694 909 1 011 812 247 803 48 119 195 529 520 361 341 968 138 328 79 054 124 586 2 a 10 anos 26 862 597 10 136 749 2 547 172 473 776 1 959 026 5 156 775 3 459 433 1 381 807 785 546 1 292 080

Figure 1: Population for Southeast and South Brazil from the Brazilian Institute of Geography and Statistics the information is from the 2010 Census.

A high reactive Nitrogen level in surface water is a well-known issue and has been widely researched in literature as well as more specifically to the Piracicaba River area. Literature in BPWN application is very limited, and research for this application varies vastly from the geographical location of our target area. The literature review will outline Nitrogen literature first and how it relates and differentiates from the proposed project and then move to BPWN and what modifications are necessary to implement in the target environment, geography, and utilization. To better understand the similarities and differences from this proposed project to other studies in the past, a closer look at the target area is provided below.

Fernandez Smithers 6

Figure 1: Targeted area in the Piracicaba River basin circled

The four target sugarcane plantations are: Usina Diamante in Ja, So Paulo Usina Costa Pinto in Piracicaba, So Paulo Usina Rafard in Rafard, So Paulo Usina Santa Helenain Rio das Pedras, So Paulo

These were selected based on geographical proximity to the basin. This is an important factor because it will be much easier to differentiate between what Nitrogen is actually coming from the plantation and its respective fertilizer and what Nitrogen is coming from urban sewage and other waste. Keeping the testing site confined to four plantations will also make for a more feasible potential BPWN analysis. When actual implementation occurs, the political and social aspect will also be easier to manage. A water availability study in 2011 shows the growing demand for water quantity from the Piracicaba River and its tributaries (Orellana Gonzalez, et al). As this demand continues to grow, and reactive Nitrogen discharge levels not only not decrease, but actually increase, the overload in the water will be unsustainable unless something changes. Higher water utilization rates and higher discharge rates together will drastically influence nutrient concentration in the river, and this overloaded system will impact not only fish and fauna, but human health in

Fernandez Smithers 7 southeast So Paulo as well. High pollution levels have already been determined in the Atibaia River portion of the basin, linked to industrial effluents, agricultural activity, and urban sewage (Favaro, et al). The area tested in the Favaro study is a highly urban area with many large cities and little to no wastewater treatment before direct discharge into the river. A very good study exists on the effects of land use done in two catchments of the basin, one found of the western-most part of the area targeted in this study. One of the two catchments (Pisca) analyzed an area that was 62% used by sugar cane plantation at the time of the study (Ometo, et al). Though land use of this particulate area has not changed a significant amount, fertilizing and harvesting practices have dramatically changed, and thus this study is no longer useful for purposes of proper planning for Nitrogen availability for agricultural recycle. Nitrogen input in the Piracicaba basin was very thoroughly identified in a 2003 study. The study was careful to consider the whole basin region and accounted for all anthropogenic reactive Nitrogen including sewage discharge, all crop types with their specific fertilizer requirements, net atmospheric deposition, imported food, and industrial waste (Filoso, et al 2003). The study also implemented methods to subtract natural Nitrogen from their total account, as well as determining what background levels may have accumulated from past events. While this study is extremely helpful and very well presented, it would be nearly impossible to use for a BPWN design as it includes all Nitrogen sources, and using watershed from all the region to redirect to agricultural recycle would a) not be a feasible scope project and b) would dangerously decrease the river water level, which would of course only further the water quality problem. That being said, looking at sugarcane plantations directly is useful because much of the atmospheric Nitrogen actually reaches the sugarcane land more directly than the water itself, so the watershed from these plantations straight to the river are an important addition to the water that would not normally exist. In a study on reactive Nitrogen deposition, sugarcane is shown to play a key role in dry deposition. This is shown in Figure 2 below (Allen, et al., 2011).

Fernandez Smithers 8

Figure 2: Annual deposition fluxes of NO2-N, HNO3-N, NH3-N, NO3--N and NH4+-N to tropical

forest, sugar cane and water surfaces Since more Nitrogen compounds are deposed in the sugarcane, more will eventually enter the river flow as the crops are irrigated and that water enters the plantation watershed straight for the Piracicaba River. Global trends show movement towards larger quantities of Nitrogen fertilizers, driven by the huge increase in demand for all types of agriculture, from food to biofuels. The graph below shows the relationship of Nitrogen fertilizers and irrigated land (Tilman 2002). This is such a key issue, even leading into the turn of the century. As the graph clearly shows, Nitrogen is not only increasing, the danger lies when it is overly applied so that it overloads the ecosystem.

Fernandez Smithers 9

Figure 3: Total global use of nitrogen and phosphorus fertilizer (former USSR not included) and area of global irrigated land.

Fertilizations practices are changing every year, especially as Brazils production of biofuels is on the rise to meet a growing global demand. Already, several studies have been published on the efficiency of Nitrogen fertilization and ways to improve efficiency and therefore reduce waste (Azeredo et al., 1986; Carnaba, 1990; Orlando Filho et al., 1999; Urquiaga et al., 1992). Brazil has really shifted from being a developing nation to being a leader in exports, political advancements, and even technological research in the last few years. With this comes a rapid growth and a desire to produce more and invest in new technologies. While this can be a very positive thing for Brazil, and the Piracicaba basin specifically, it can also turn into a dangerous game if satisfactory infrastructure does not support the rapid growth. For example, while sugarcane harvest is still done by hand and low-power machines, the practice of burning the fields for easier harvest will continue, which has been shown to reduce the efficiency of Nitrogen intake by the ratoon (Azeredo et al., 1986; Salcedo and Sampaio, 1984). Overfertilization is common, then, when demand is greater because farmers tend to prefer to err on the side of over-fertilization, therefore, allowing more waste of reactive Nitrogen to enter the watershed. This is a particular reason for why a remediation is in need.

Fernandez Smithers 10 On that note, the Piracicaba River basin does not have a history of abiding by recommendation or even laws mandated by the city for things such as outlawing chemicals or treating sewage, etc. For example , although nearly all the households in the basin area had a working sewage system, only 16% of the domestic sewage was actually treated in 2003 (Filoso, et al., 2003). Even years later after they were banned from use, there is evidence of organochlorine pesticides being used and discharged directly into the river, and obviously affecting the fish population in the river, and, possibly, human health because of high consumption of the fish in that area. This just reinforces that fact that a recycle remediation is an important consideration even if more efficient fertilization recommendations are made. Baojing Gu, et al. have done the most extensive research in the Biofuel Production using Waste Nitrogen method in China. They have outlined some advantages of implementing BPWN as follows, as found in Utilization of waste nitrogen for biofuel production in China (Gu, et al., 2011): (1) There is no need for N fertilizer application and so it can reduce the cost of energy input and increase the net energy balance ratio (NER, Output/Input). (2) BPWN can reduce environmental N pollution, the cost of pollution control and greenhouse gas (GHG) emissions since there is no need for the waste N to be treated via treatment facilities, e.g. wastewater treatment plant (WTP). (3) Waste N is coupled to water supply, such as domestic wastewater, and the effluent water can be reused for irrigation; therefore, there is less water deficiency stress on BPWN. (4) BPWN can use untilled or marginal land and so can avoid competing with food production on fertile soils. (5) BPWN can also provide other ecosystem services, including renewal of soil fertility, and avoiding health risks since if the waste N is not being used for biofuel production, it might be used for agricultural food production instead. Clear modifications will be made for use in southeast Brazil rather than the space of one of the largest countries in the world. There is very limited land use for food crops, so implementing BPWN would essentially be easier and safer than in the studied region in China, but there is also limited land that could be used to expand the targeted site area in Piracicaba because of moderately high domestic use and

Fernandez Smithers 11 expected growth. There is also the question of how much the intended project would be able to combine domestic wastewater for agricultural irrigation because of the dependency of river flow of the river as being an important tributary of other major rivers. The role of technology and policy in mitigating regional nitrogen pollution is another article that delineates the method for BPWN potential analysis (Gu, et al., 2011). The parameters shown in this study would be used as a rough outline for the proposed study, but would need to be greatly modified to meet the vastly different needs and resources available in the targeted region. It will also yield smaller results simply due to the fact that we would not consider, at least for the current scope of the project not considering expansion, parameters such as population, livestock, and urban sewage. Although the design would not use urban sewage (at least initially), it is probable that Nitrogen is actually being added through non-fertilizers in large quantities, and BPWN would actually take advantage of these non-point sources by combining them in the watershed. A study on Brazilian sugarcane field conditions suggests that more than half of the Nitrogen run-off from ethanol plantations is from a source other than the fertilizer. This is shown in Figure 3 below (Junqueira Franco, et al., 2010).

Figure 4: N derived from fertilizer (NDFF) or from other sources (Nother sources) in sugarcane nutrition during the plant cane crop cycle.

Fernandez Smithers 12 In these charts, the black shaded source is non-fertilizer Nitrogen, and the while-shaded is Nitrogen derived from fertilizer (NDFF) for two ethanol plantations in Brazil, So Luiz and Santa Adlia, both around 100km North of the Piracicaba basin. This study supports the prediction that BPWN has a very high potential in this tropical part of Brazil. C. Methods, Procedures, and Facilities Water samples will be collected from the time of grant approval for two years at eight sampling stations. Each target plantation will have two sampling stations at major watershed locations that directly discharge to the Piracicaba River. To reduce costs and to get a better idea of Nitrogen average levels, weekly samples will be taken. The first month of these will be done by the lead graduate research assistant for the project under the supervision and guidance of the post-graduate researcher. The next month sampling will be done by two undergraduate research assistants from the Universidade Metodista de Piracicaba (UNIMEP) under the supervision and guidance of the lead graduate research assistant. Then all sampling will be executed by the UNIMEP undergraduates for the next 22 months, with the graduate research assistant coming when necessary, most likely every six months. With every sample, flow rate will also be measured at the location. Following the procedure done by Solange Filoso, et al. in Land use and nitrogen export in the Piracicaba River basin, Southeast Brazil, samples will be collected from watershed surface (30 cm) with a Nalgene bottle and then will be stored in ice in the dark, using a simple cooler, while transported to the UNIMEP laboratory. Nitogen samples will be filtered through cellulose acetate filters with a nominal pore size of 0.45 m. Filtering will be done once in the environmental laboratory and will be stored at 4C before actual analysis. Determination of Nitrogen concentration will be gathered from the samples being run in a Shimatzu ion chromatograph, available for use in the UNIMEP laboratory. Simultaneously to sampling time, from months 2 to 24, the lead graduate research assistant will map elevation of the target sugarcane plantation area using GIS and simple elevation profiling from Google Earth-Pro. This, along with the flow rate data, can be utilized to design a water distribution system that will re-fertilize segments of each of the four plantations, with the option of expansion, depending on land availability.

Fernandez Smithers 13 References Allen, A.G., Machado, C.M.D., and Cardoso, A.A. (2011). Measurements and modeling of reactive nitrogen deposition in southeast Brazil. Environmental Pollution 159: 1190-1197. Allen, R.G., Pereira, L.S., Raes, D., Smith, M. (1998). Crop Evapotranspiration: Guidelines for Computing Crop Water Requirements. FAO, Rome. FAO Irrigation and Drainage Paper: 56. Favaro, P.C., De Nadai Fernandes, E.A., Ferraz, E.S.B., and Faltico, M.H.B. (2004). Time still to restore the polluted Piracicaba river basin. Journal of Radioanalytical and Nuclear Chemistry, Vol. 259, No. 2: 217-221. Filoso, S., Martinell,i L.A., Williams M.R., Lara, L.B., Krusche, A., Ballester, M.V., Victoria, R., and De Camargo, P.B. (2003). Land use and nitrogen export in the Piracicaba River basin, Southeast Brazil. Biogeochemistry 65: 275294. Franco, H.C.J., Otto, R., Faroni, C.E., Vitti, A.C., De Oliveira, E.C.A., and Trivelin, P.C.O. (2011). Nitrogen in sugarcane derived from fertilizer under Brazilian field conditions. Field Crops Research 121: 2941. Godfrey, B. J. (1999). Brazil. Focus on Geography, 45(4), 1-28. http://search.proquest.com/docview/198480473?accountid=6667 Gu, B., Liu, D., Wu, X., Ge, Y., Min, Y., Jiang, H., and Chang, J. (2011). Utilization of waste nitrogen for biofuel production in China. Renewable & Sustainable Energy Reviews, 15(9): 4910-4916. Gu, B., Zhu, Y., Chang, J., Peng C., Liu, D., Min, Y., Luo, W., Howarth, R.W., and Ge, Y. (2011). The role of technology and policy in mitigating regional nitrogen pollution. Environ Res Lett 6: 014011. Heffer, P and Prudhomme, M. (2011). 79th IFA Annual Conference Montreal (Canada). International Fertilizer Industry Association (IFA): May 23-25, 2011. Knobeloch, L., Salna, B., Postle, J., and Anderson, H. (2000). Blue Babies and NitrateContaminated Well Water. Environ Health Perspect 108: 675-678. Ometo, J.P.H.B, Martinelli, L.A., Ballester, M.V., Gessner, A., Krusche, A.V., Victoria, R.L. and Williams, M. (2000). Effects of land use on water chemistry and macroinvertebrates in two streams of the Piracicaba river basin, south-east Brazil. Freshwater Biology 44: 327337.

Fernandez Smithers 14 Orellana-Gonzlez, A.M.G., Snchez-Romn, R.M., Folegatti, M.V., and Zolin, C.A. (2011). PCJ River BasinsWater Availability Caused by Water Diversion Scenarios to Supply Metropolitan Areas of So Paulo. Water Resour Manage 25:33713386. Resultados Preliminares do Universo do Censo Demogrfico. (2010). Instituto Brasileiro de Geografia e Estatisticas: Tabela 1. <http://www.ibge.gov.br/home/estatistica/populacao/censo2010/resultados_preliminares/pr eliminar_tab_uf_zip.shtm> Schrope, M. (2006). The Dead Zones. New Scientist 192, 2581: 38-42. Tilman, D., Cassman, K.G., Matson, P.A., Naylor, R., and Polasky, S. (2002). Agricultural sustainability and intensive production practices. Nature, 418(6898): 671. Why is Eutrophication Such a Serious Pollution Problem? Lakes and Reservoirs 3.

Fernandez Smithers 15 Budget

Expense Graduate research assistant (GRA), academic year GRA, summer GRA travel, air GRA travel, ground Rate $1,300 per month Duration Nine months Total $11,700

Post graduate research assistant (PGRA) PGRA travel, air PGRA travel, ground 2 Undergraduate assistants Field sampling equipment - 1-L bottles - Filters - Stopwatch - Syringes - Cooler Mapping supplies - Google EarthPro Office expenses

$2,600 per month $1,100 per round-trip $100 per week - 2 $25 bus - Gas - Taxi - Tolls $400 per week $1,100 per round-trip $50 per week $8.20/ hour each Store prices estimate, average

3 months 6 trips 6 weeks

$7,800 $6,600 $600

2 week 2 trips 2 weeks 5 hours/week for 23 months Enough for 2 year study

$800 $2,200 $100 $7544 $850

$399 per user per year

1 user for 2 years

$798

Trip miscellaneous expenses In-state student fee Total

Estimate for phone use, printing, copying, staples, pencils, etc. Estimate for lunches, thank you notes, beverages, etc. $7,500 per year

2 years

$500

6 trips

$750

2 years

$15,000 $55,242.000