Production of bio-oil from algal biomass and its upgradation to biodiesel using CaO-based heterogeneous catalysts

The present article deals with the production of bio-oil from algal biomass as well as the preparation and characterization of noble CaO-based heterogeneous catalyst for upgradation of bio-oil to biodiesel. The bio-oil has been extracted from algal biomass using hexane as solvent in soxhlet apparatus and upgraded to biodiesel by transesterification using noble CaO-based heterogeneous catalysts. Catalyst with TiO₂:CaO molar ratio of 0.25 and calcination temperature of 700°C has been found to be most suitable among all the catalysts developed. Characterization of the catalysts has been done by using X-ray diffraction (XRD), scanning electron microscope (SEM), and thermo-gravimetric analysis (TGA). The input--output model has been developed to correlate experimental and predicted value of biodiesel yield. Optimization of process parameters has been done using response surface methodology. Various properties and elemental composition of algal bio-oil and biodiesel have been determined and compared with biodiesel.     

ALGAE IN THE SPOON RIVER,ILLINOIS 1971–19721

ABSTRACT: As a part of a water quality survey of the Spoon River, Illinois, algal genera were identified and their densities were enumerated. Weekly samples were collected at five stations starting on June 1, 1971. This report presents the first year's results. Algal densities for each station were found to be distributed geometrically normal. Total algal densities increased as water progressed downstream. Although water temperature has been observed to be an important factor affecting the density and the composition of algae in streams, attempts to correlate algal densities with temperatures for the Spoon River were not fruitful. Correlations of algal densities with dissolved oxygen, flow, and coliform densities also could not be made. The dominant genera observed were Cyclotella, Navicula, Scenedesmus, and Euglena. On the average diatoms accounted for 87% of all algae counts. The average diversity indices varied about 1.0 to 1.5 for five stations. There did not appear to be any advantage in the use of diversity index over that of algal density and genera richness in characterizing algae in the Spoon River.     

USING HEAT CAPACITY MAPPING MISSION (HCMM) DATA TO ASSESS LAKE WATER QUALITY1

ABSTRACT A water quality investigation on Utah Lake was conducted during the same time period that the Heat Capacity Mapping Mission (HCMM) satellite was collecting thermal infrared and reflectivity data. Relationships were established and evaluated among HCMM data and lake water quality parameters. Although remotely sensed reflective data have been previously utilized, this study was unique in that thermal emitted data were also correlated to algae concentrations and other indicators. Standard statistical evaluations were made along with utilization of color graphics techniques to identify and plot relationships. The emitted thermal energy was found to have high positive correlations with net algal concentrations and with the predominant species, Aphanizomenon flos-aquae, a blue-green alga. No continuous correlation was found for a less abundant red pigment phytoplankton, Ceratium hirundinella. Similar trends, though for negative correlations, were shown for reflectivity data and algal concentrations throughout the spring and summer. Coincidence of areas of warmer emitted energy and darker relfected energy on colorgraphics displays clearly indicate lake areas of high algal concentrations. Night thermal data displayed a strong negative correlation with algal concentration, opposite to day thermal data. Color graphics of warmer day emitted energy and cooler night emitted energy further verify areas of high algal concentrations.     

PHYTOPLANKTON IN THE FOX CHAIN OF LAKES1

ABSTRACT: As part of a comprehensive water quality investigation on the Fox Chain of Lakes during May to October 1975, water samples from the Chain and Cedar Lake (reference) at 25 locations were collected weekly or bi-weekly to determine the species and densities of algae. The results have been evaluated for algal composition, density, and succession for each location. Sixty-four algal species were recovered from 414 samples. The number of species per sampling location varied from 10 at Channel Lake and Lake Marie to 26 on Fox Lake (main) and Grass Lake. Blue green algae were predominant and occurred at 25 of the 25 sampling stations. They consisted mainly of Aphanizomenon flos-aquae. The only flagellate of importance was Ceratium hirundinella, and significant concentrations of this organism were limited to Channel Lake and Lake Catherine. The only green alga bloom was created by Ulothrix variabilis on the waters of Pistakee Lake. Diatoms were quite significant on the shallower water bodies. Algal densities ranged from about 25 to 14,000 cts/ml. The highest count occurred on Mineola Bay. Other high counts (>10,000 cts/ml) observed were waters taken from Channel Lake, Grass Lake, and Fox Lake (main). In Grass Lake, 60 percent of the collections had algal densities in excess of 2,000 cts/ml. Most of these were the diatom Cyclotella meneghiniana.     

Valuing algal bloom in the Black Sea Coast of Bulgaria: A choice experiments approach

Increased interest in water quality in coastal and marine areas stemming from the Water Framework Directive and the Marine Strategy Framework Directive has led to important questions in relation to policies that address nutrient loadings. This paper presents the results from a choice experiment study to assess the recreational damage associated with algal blooms caused by nutrients flows into Varna Bay, Bulgaria. Varna Bay is an important beach destination on the Black Sea coast of Bulgaria. Algal bloom events have been experienced frequently in the area. A choice experiment questionnaire was developed and applied in the Varna Bay area to assess the extent to which the quantity of algal blooms and the duration of the bloom affect recreational activities. The amount of bloom was found to be important, as respondents were on average willing to pay a one off tax of 18.97 Leva (€9.73) for a program that provides beaches free from algal blooms.     

Sludge-grown algae for culturing aquatic organisms: Part I. Algal growth in sludge extracts

This project is aimed at studying the feasibility of using sewage sludge to prepare culture media for microalgae (Chlorella-HKBU) and the use of the sludge-grown algae as a feed for some aquatic organisms. Part I of the project included results on preparing sludge extracts and their use on algal culture. By comparing two culturing techniques, aeration and shaking, it was noted that both lag and log phases were shortened in the aeration system. A subsequent experiment noted that algal growth subject to aeration rates of 1.0 and 1.5 liters/min had similar lag and log phases. In addition, both aeration rates had a significantly higher (P < 0.05) final cell density than that of 0.5 liters/min. A detailed study on the variation of growth conditions on the algal growth was done. The results indicated that pH values of all the cultures declined below 5 at day 12. The removal rates of ammonia N ranged from 62% to 70%. The sludge-grown algae contained a rather substantial amount of heavy metals (µg/g): Zn 289–581, Cu 443–682, Ni 310–963, Mn 96–126, Cr 25–118, and Fe 438–653. This implied that the rather high levels of heavy metals may impose adverse effects on higher trophic organisms.     

CuSO4 treatment of nuisance algal blooms in drinking water reservoirs

Since the turn of the century, copper sulfate has been used extensively as an algicide to control nuisance algal blooms in drinking water reservoirs Recent experimental results have shown that the toxicity of copper to algae is determined by the activity of ionic copper, and not the total copper concentration The sensitivity of algae to ionic copper has been found to vary considerably for different algal species Chemical processes such as precipitation, complexation by dissolved organic substances, and adsorption by suspended material can be important in controlling the chemical speciation of copper added to drinking water reservoirs The copper sulfate dosage required for effective treatment of a reservoir is shown to depend on water chemistry and the copper sensitivity of nuisance algal species By evaluating copper chemistry and copper sensitivity of nuisance algal species it may be possible to obtain effective treatment with lower copper sulfate dosages in some reservoirs     

THE POTENTIAL EFFECTS OF GLOBAL WARMING ON THE PRIMARY PRODUCTIVITY OF A SUBALPINE LAKE1

ABSTRACT Atmospheric scientists have predicted that large-scale climatic changes will result from increasing levels of tropospheric CO₂ We have investigated the potential effects of climate change on the primary productivity of Castle Lake, a mountain lake in Northern California. Annual algal productivity was modeled empirically using 25 years of limnological data in order to establish predictive relationships between productivity and the climatic variables of accumulated snow depth and precipitation. The outputs of monthly temperature and precipitation from three general circulation models (GCMs) of doubled atmospheric CO₂ were then used in the regression model to predict annual algal productivity. In all cases, the GCM scenarios predicted increased algal productivity for Castle Lake under cenditions of doubled atmospheric CO₂The primary cause of enhanced productivity was the increased length of the growing season resulting from earlier spring ice-out.     

Autoclaving soil samples affects algal-available phosphorus

Unwanted microbial interference in samples used for biological assays of P availability has routinely been eliminated by autoclaving samples before inoculation with algae. Twenty-three soils were selected to evaluate the relationship between algal growth in P-deficient solutions containing small quantities of soil and the level of P determined by a variety of tests used to evaluate P availability in soils and sediments. Soils were either autoclaved or not before addition to flasks containing P-starved algae in a nutrient solution without P. Compared to non-autoclaved samples, autoclaving soil resulted in approximately 60% more available P as estimated by increased algal growth. However, algal growth in the presence of autoclaved soil was highly correlated with growth in the presence of non-autoclaved samples. There was no consistent change in the correlations (r) between autoclaving or non-autoclaving samples in the relationships of algal numbers with P extracted by a number of soil tests. The effect of autoclaving soil on soluble P was also evaluated for a subset of six soils. Autoclaved soils had significantly greater concentrations of soluble P than non-autoclaved soils, with 78% more orthophosphate monoesters, 60% more orthophosphate diesters, and 54% more soluble inorganic P. Inhibition of algal growth may have occurred with two high-Zn soils that produced relatively low numbers of algae despite being very high in estimated available P by all extraction methods. Removing those samples from the calculations dramatically improved correlations between soil P measured by various methods and algal growth. With these two soils removed from calculations, algal growth with autoclaved soil was most highly correlated with Olsen P (r = 0.95), with other correlations as follows: Fe-oxide strip (r = 0.80), Mehlich 3 (r = 0.75,), modified Morgan (r = 0.61), and Bray-Kurtz 1 (r = 0.57).     

Model‐Based Nitrogen and Phosphorus (Nutrient) Criteria for Large Temperate Rivers: 2. Criteria Derivation

Nitrogen and phosphorus criteria were developed for 233 km of the Yellowstone River, one of the first cases where a mechanistic model has been used to derive large river numeric nutrient criteria. A water quality model and a companion model which simulates lateral algal biomass across transects were used to simulate effects of increasing nutrients on five variables (dissolved oxygen, total organic carbon, total dissolved gas, pH, and benthic algal biomass in depths ≤1 m). Incremental increases in nutrients were evaluated relative to their impact on predefined thresholds for each variable; the first variable to exceed a threshold set the nutrient criteria. Simulations were made at a low flow, the 14Q5 (lowest average 14 consecutive day flow, July‐September, recurring one in five years), which was derived using benthic algae growth curves and EPA guidance on excursion frequency. An extant climate dataset with an annual recurrence was used, and tributary water quality and flows were coincident with the river's 10 lowest flow years. The river had different sensitivities to nutrients longitudinally, pH being the most sensitive variable in the upstream reach and algal biomass in the lower. Model‐based criteria for the Yellowstone River are as follows: between the Bighorn and Powder river confluences, 55 μg TP/l and 655 μg TN/l; from the Powder River confluence to Montana state line, 95 μg TP/l and 815 μg TN/l. Pros and cons of using steady‐state models to derive river nutrient criteria are discussed.     

Response of Algal Biomass to Large‐Scale Nutrient Controls in the Clark Fork River,Montana, United States1

Suplee, Michael W., Vicki Watson, Walter K. Dodds, and Chris Shirley, 2012. Response of Algal Biomass to Large‐Scale Nutrient Controls in the Clark Fork River, Montana, United States. Journal of the American Water Resources Association (JAWRA) 48(5): 1008‐1021. DOI: 10.1111/j.1752‐1688.2012.00666.x Abstract: Nutrient pollution is an ongoing concern in rivers. Although nutrient targets have been proposed for rivers, little is known about long‐term success of programs to decrease river nutrients and algal biomass. Twelve years of summer data (1998‐2009) collected along 383 km of the Clark Fork River were analyzed to ascertain whether a basin‐wide nutrient reduction program lowered ambient total nitrogen (TN) and total phosphorus (TP) concentrations, and bottom‐attached algal biomass. Target nutrient and algal biomass levels were established for the program in 1998. Significant declines were observed in TP but not TN along the entire river. Downstream of the city of Missoula, TP declined below a literature‐derived TP saturation breakpoint and met program targets after 2005; TN was below targets since 2007. Algal biomass also declined significantly below Missoula. Trends there likely relate to the city’s wastewater facility upgrades, despite its 20% population increase. Upstream of Missoula, nutrient reductions were less substantial; still, TP and TN declined toward saturation breakpoints, but no significant reductions in algal biomass occurred, and program targets were not met. The largest P‐load reduction to the river was from a basin‐wide phosphate laundry detergent ban set 10 years before, in 1989. We document that nutrient reductions in rivers can be successful in controlling algal biomass, but require achievement of concentrations below saturation and likely close to natural background.     

Tiny Stowaways: Analyzing the Economic Benefits of a U.S. Environmental Protection Agency Permit Regulating Ballast Water Discharges

The U.S. Environmental Protection Agency has proposed permitting ballast water discharges—a benefit of which would be to reduce the economic damages associated with the introduction and spread of aquatic invasive species. Research on ship-borne aquatic invasive species has been conducted in earnest for decades, but determining the economic damages they cause remains troublesome. Furthermore, with the exception of harmful algal blooms, the economic consequences of microscopic invaders have not been studied, despite their potentially great negative effects. In this paper, we show how to estimate the economic benefits of preventing the introduction and spread of harmful bacteria, microalgae, and viruses delivered in U.S. waters. Our calculations of net social welfare show the damages from a localized incident, cholera-causing bacteria found in shellfish in the Gulf of Mexico, to be approximately $706,000 (2006$). On a larger scale, harmful algal species have the potential to be transported in ships’ ballast tanks, and their effects in the United States have been to reduce commercial fisheries landings and impair water quality. We examine the economic repercussions of one bloom-forming species. Finally, we consider the possible translocation within the Great Lakes of a virus that has the potential to harm commercial and recreational fisheries. These calculations illustrate an approach to quantifying the benefits of preventing invasive aquatic microorganisms from controls on ballast water discharges. The views expressed in this paper are those of the authors and do not necessarily reflect the views or policies of the U.S. Environmental Protection Agency.     

Methane emission from rice paddy soils, aerotolerance of methanogens and global thermal warming

In vitro methane emissions from different rice paddy soils and algal mats were studied under anoxic and atmospheric conditions. Methane production from rice paddy soils cultivating different strains of rice was found to be appreciable under anoxic conditions, but considerably reduced under atmospheric conditions, and dependent on rice cultivars (strains). A contradictory result was obtained with a Gobindabhog cultivated rice field (a strain of rice with aroma), where methane yield under anoxic was greater than that under atmospheric conditions. The results indicated aerotolerance of methanogens or the possible existence of microaerophilic methanogens. The results from algal mats corroborated these findings.Methane has been considered to be an important greenhouse gas contributing significantly to global thermal warming (GTW). Flooded rice paddy fields have been considered to be a most prominent source of abiogenic methane emission, though considerable uncertainty exists regarding the true estimates of methane emission. Factors affecting methane emission and its abatement have been examined. In spite of increasing methane emission, rice cultivation leads to enormous utilization of the green house gas carbon dioxide and release of oxygen to the atmosphere. Thus, the contribution of methane to GTW (from rice paddy cultivation) is more than compensated by carbon dioxide absorption.Appropriate steps have been suggested for the reduction of methane emissions, the most important of which is the restoration of methane sinks.     

EFFECTS OF SEDIMENTATION ON THE ALGAL FLORA OF A SMALL RECREATIONAL IMPOUNDMENT1

ABSTRACT: Investigations were initiated to evaluate the effects of sedimentation on the algal composition, primary productivity rates and chemical nutrient concentrations of a 17 acre recreational impoundment in central Virginia. Comparisons during the winter seasons of 1972–1973 indicated that as a result of sedimentation, from lake front home construction, the total numbers of algal genera in the lake decreased from 24 to 16, productivity as measured by ¹⁴CO₂ and total extractable chlorophyll decreased two fold, and several important nutrients, i.e. NH4⁺-N, SiO₂ and PO₄-P increased significantly.     

The Influence of Nutrients and Physical Habitat in Regulating Algal Biomass in Agricultural Streams

This study examined the relative influence of nutrients (nitrogen and phosphorus) and habitat on algal biomass in five agricultural regions of the United States. Sites were selected to capture a range of nutrient conditions, with 136 sites distributed over five study areas. Samples were collected in either 2003 or 2004, and analyzed for nutrients (nitrogen and phosphorous) and algal biomass (chlorophyll a). Chlorophyll a was measured in three types of samples, fine-grained benthic material (CHL_FG), coarse-grained stable substrate as in rock or wood (CHL_CG), and water column (CHL_S). Stream and riparian habitat were characterized at each site. TP ranged from 0.004–2.69 mg/l and TN from 0.15–21.5 mg/l, with TN concentrations highest in Nebraska and Indiana streams and TP highest in Nebraska. Benthic algal biomass ranged from 0.47–615 mg/m², with higher values generally associated with coarse-grained substrate. Seston chlorophyll ranged from 0.2–73.1 μg/l, with highest concentrations in Nebraska. Regression models were developed to predict algal biomass as a function of TP and/or TN. Seven models were statistically significant, six for TP and one for TN; r ² values ranged from 0.03 to 0.44. No significant regression models could be developed for the two study areas in the Midwest. Model performance increased when stream habitat variables were incorporated, with 12 significant models and an increase in the r ² values (0.16–0.54). Water temperature and percent riparian canopy cover were the most important physical variables in the models. While models that predict algal chlorophyll a as a function of nutrients can be useful, model strength is commonly low due to the overriding influence of stream habitat. Results from our study are presented in context of a nutrient-algal biomass conceptual model.     

Integrating Seasonal Information on Nutrients and Benthic Algal Biomass into Stream Water Quality Monitoring

Benthic chlorophyll a (BChl a) and environmental factors that influence algal biomass were measured monthly from February through October in 22 streams from three agricultural regions of the United States. At‐site maximum BChl a ranged from 14 to 406 mg/m² and generally varied with dissolved inorganic nitrogen (DIN): 8 out of 9 sites with at‐site median DIN >0.5 mg/L had maximum BChl a >100 mg/m². BChl a accrued and persisted at levels within 50% of at‐site maximum for only one to three months. No dominant seasonal pattern for algal biomass accrual was observed in any region. A linear model with DIN, water surface gradient, and velocity accounted for most of the cross‐site variation in maximum chlorophyll a (adjusted R² = 0.7), but was no better than a single value of DIN = 0.5 mg/L for distinguishing between low and high‐biomass sites. Studies of nutrient enrichment require multiple samples to estimate algal biomass with sufficient precision given the magnitude of temporal variability of algal biomass. An effective strategy for regional stream assessment of nutrient enrichment could be based on a relation between maximum BChl a and DIN based on repeat sampling at sites selected to represent a gradient in nutrients and application of the relation to a larger number of sites with synoptic nutrient information.     

Do Nutrients Limit Algal Periphyton in Small Blackwater Coastal Plain Streams?1

Abstract: We examine the potential for nutrient limitation of algal periphyton biomass in blackwater streams draining the Georgia coastal plain. Previous studies have investigated nutrient limitation of planktonic algae in large blackwater rivers, but virtually no scientific information exists regarding how algal periphyton respond to nutrients under different light conditions in smaller, low‐flow streams. We used a modification of the Matlock periphytometer (nutrient‐diffusing substrata) to determine if algal growth was nutrient limited and/or light limited at nine sites spanning a range of human impacts from relatively undisturbed forested basins to highly disturbed agricultural sites. We employed four treatments in both shaded and sunny conditions at each site: (1) control, (2) N (NO₃‐N), (3) P (PO₄‐P), and (4) N + P (NO₃‐N + PO₄‐P). Chlorophyll a response was measured on 10 replicate substrates per treatment, after 15 days of in situ exposure. Chlorophyll a values did not approach what have been defined as nuisance levels (i.e., 100‐200 mg/m²), even in response to nutrient enrichment in sunny conditions. For Georgia coastal plain streams, algal periphyton growth appears to be primarily light limited and can be secondarily nutrient limited (most commonly by P or N + P combined) in light gaps and/or open areas receiving sunlight.     

A SEDIMENT RESUSPENSION AND WATER QUALITY MODEL OF LAKE OKEECHOBEE1

ABSTRACT: The influence of sediment resuspension on the water quality of shallow lakes is well documented. However, a search of the literature reveals no deterministic mass-balance eutrophication models that explicitly include resuspension. We modified the Lake Okeechobee water quality model - which uses the Water Analysis Simulation Package (WASP) to simulate algal dynamics and phosphorus, nitrogen, and oxygen cycles - to include inorganic suspend. ed solids and algorithms that: (1) define changes in depth with changes in volume; (2) compute sediment resuspension based on bottom shear stress; (3) compute partition coefficients for ammonia and ortho-phosphorus to solids; and (4) relate light attenuation to solids concentrations. The model calibration and validation were successful with the exception of dissolved inorganic nitrogen species which did not correspond well to observed data in the validation phase. This could be attributed to an inaccurate formulation of algal nitrogen preference and/or the absence of nitrogen fixation in the model. The model correctly predicted that the lake is light-limited from resuspended solids, and algae are primarily nitrogen limited. The model simulation suggested that biological fluxes greatly exceed external loads of dissolved nutrients; and sediment-water interactions of organic nitrogen and phosphorus far exceed external loads. A sensitivity analysis demonstrated that parameters affecting resuspension, settling, sediment nutrient and solids concentrations, mineralization, algal productivity, and algal stoichiometry are factors requiring further study to improve our understanding of the Lake Okeechobee ecosystem.     

Relationships among nutrients, chlorophyll-a, and dissolved oxygen in agricultural streams in Illinois

A better understanding of the controls on algae and dissolved O2 in agricultural streams of Illinois is needed to aid in development of nutrient standards. We investigated the relationships between dissolved nutrients, algal abundance, and dissolved O2 in five streams in east-central Illinois from March through November 2004. The streams drained watersheds from 25 to 777 km2 that were dominated by row crop agriculture. Three sites had open canopies and two were bordered by a narrow forest of deciduous trees. Algal abundance was measured as chlorophyll-a (chl-a) concentration in the water column (sestonic) and on the streambed (periphytic). Mean NO3-N concentrations ranged from 5.5 to 8.8 mg N L(-1) and did not relate to algal abundance. Sestonic chl-a values ranged from nearly zero to >15 mg m(-3) with no differences between open and shaded streams and only a weak correlation with dissolved reactive P (mean concentrations were 44-479 microg L(-1)). The results suggest that sestonic chl-a is a poor criterion for assessing nutrient-related problems in these streams. Greatest periphytic chl-a occurred during low flow from August through October, but periphyton occurred consistently in only two of the five streams. The abundance of filamentous algae explained 64% of the variation in diel O2 saturation, but was not correlated with nutrients. Currently it appears that hydrology and light, rather than nutrients, control algal abundance in these streams, and in the agricultural landscape of east-central Illinois, it may not be possible to reduce nutrient concentrations sufficiently to limit filamentous algal blooms.     

ALGAL BLOOM PROBABILITY IN A LARGE SUBTROPICAL LAKE1

ABSTRACT: Algal blooms, defined as chlorophyll α concentrations greater than 40 μg l^?1, are common in Lake Okeechobee, Florida. Using logistic regression techniques, we have developed equations that relate limnological variables to algal bloom occurrence in four distinct open-water regions of this large shallow lake: central pelagic, northwest, southwest, and a transition region between the western and pelagic regions. Wind velocity and total phosphorus, which are closely related to resuspended material in the central region, are negatively related to algal bloom occurrence there. In the transition region, algal bloom occurrence is positively related to total nitrogen and wind velocity. Algal bloom occurrence is strongly and positively related to total nitrogen and total phosphorus concentrations in the western regions. The logistic regression model predicts an algal bloom probability greater than 95 percent in the northwest region when total phosphorus exceeds 0.10 mg l^?1 and total nitrogen exceeds 2.5 mg l^?1. In the southwest region the model predicts algal bloom probability of 100 percent when total phosphorus exceeds 0.10 mg l^?1 and total nitrogen exceeds 2.8 mg l^?1. Given 1994 mean total phosphorus concentrations of 0.05 and 0.04 mg l^?1 in the northwest and southwest regions, respectively, total nitrogen would have to remain below 1.32 and 1.43 mg l^?1, respectively, to keep the algal bloom probability below 10 percent. Because the lake is heterogenous, such nutrient standards should be considered on an in-lake regional basis for Lake Okeechobee.