A mixing model analysis of stream solute dynamics and the contribution of a hyporheic zone to ecosystem function*

1. We monitored streamwater and streambed sediment porewaters from White Clay Creek (WCC), SE Pennsylvania, for dissolved organic carbon (DOC), dissolved oxygen (DO) and conductivity to investigate organic matter processing within the hyporheic zone. Dissolved organic carbon and DO concentrations were higher in the streamwater than in the porewaters and, in many cases, concentrations continued to diminish with increasing depth into the streambed. 2. Hydrological exchange data demonstrated that the permeability of the stream bed declines with depth and constrains downwelling, effectively isolating porewaters >30 cm from streamwater. 3. End‐member mixing analysis (EMMA) based on conductivity documented a DOC source and DO sink in the hyporheic zone. We calculated hyporheic streambed DOC fluxes and respiration from the EMMA results and estimates of water flux. Based upon our calculations of biodegradable DOC entering the hyporheic zone, we estimate that DOC supports 39% of the hyporheic zone respiration, with the remaining 61% presumably being supported by entrained particulate organic carbon. Hyporheic respiration averaged 0.38 g C m^?2 d^?1, accounted for 41% of whole ecosystem respiration, and increased baseflow ecosystem efficiency from 46 to 59%. 4. Advective transport of labile organic molecules into the streambed concentrates microbial activity in near‐surface regions of the hyporheic zone. Steep gradients in biogeochemical activity could explain how a shallow and hydrologically constrained hyporheic zone can dramatically influence organic matter processing at the ecosystem scale.     

Methyl <Emphasis Type="Italic">tert</Emphasis>-butyl Ether and <Emphasis Type="Italic">tert</Emphasis>-butyl Alcohol Degradation by <Emphasis Type="Italic">Fusarium solani</Emphasis>

Fusarium solani degraded methyl tert-butyl ether (MTBE) and other oxygenated compounds from gasoline including tert-butyl alcohol (TBA). The maximum degradation rate of MTBE was 16 mg protein h and 46 mg/g protein h for TBA. The culture transformed 77% of the total carbon to ¹⁴CO₂. The estimated yield for MTBE was 0.18 g dry wt/g MTBE.     

Temporal variation in organic carbon spiraling in Midwestern agricultural streams

Inland freshwaters transform and retain up to half of the carbon that enters from the terrestrial environment and have recently been recognized as important components of regional and global carbon budgets. However, the importance of small streams to these carbon budgets is not well understood due to the lack of globally-distributed data, especially from streams draining agricultural landscapes. We quantified organic carbon pools and heterotrophic metabolism seasonally in 6 low-order streams draining row-crop fields in northwestern Indiana, USA, and used these data to examine patterns in organic carbon spiraling lengths (S_OC; km), downstream velocities (V_OC; m/d), and turnover rates (K_OC; day^?1). There were seasonal differences in S_OC, with the longest spiraling lengths in winter (range: 7.7–54.4?km) and the shortest in early and late summer (range: 0.2–9.0?km). This seasonal pattern in S_OC was primarily driven by differences in discharge, suggesting that hydrology tightly controls the fate of organic carbon in these streams. K_OC did not differ seasonally, and variability (range: 0.0007–0.0193?day^?1) was controlled by differences in stream water soluble reactive phosphorus concentrations. Compared to previous studies conducted primarily in forested streams, agricultural streams tended to be less retentive of organic carbon. These systems function predominantly as conduits transporting organic carbon to downstream ecosystems, except during low, stable-flow periods (i.e., late summer) when agricultural streams can be as retentive of organic carbon as forested headwaters. High organic carbon retention in the late summer has implications for coupled carbon and nitrogen cycling (i.e., denitrification), which may play an important role in removing nitrate from stream water during periods of low flow.     

Microbial respiration within a floodplain aquifer of a large gravel-bed river

1. Aerobic respiration, productivity and the carbon turnover rate of microbial biofilms were determined at hyporheic and phreatic sites in the Kalispell Valley alluvial aquifer along a transect extending 3.9 km laterally from the main channel of the Flathead River, a sixth order river in Montana (U.S.A.). The effect of experimentally increasing bioavailable organic carbon (acetate) on the respiration rate of biofilms in this carbon‐poor [dissolved organic carbon (DOC) < 2 mg L^?1] aquifer was also measured. 2. Chambers containing natural substratum were placed in‐situ and allowed to colonise for 20 weeks. After 4, 12 and 20 weeks, they were taken to the laboratory where oxygen flux was measured in a computer‐controlled, flow‐through respirometry system. 3. Respiration ranged from 0.01 to 0.33 mg O₂ dm^?3 h^?1 across sites, with means ranging from 0.10 to 0.17 mg O₂ dm^?3 h^?1. Productivity estimates ranged from 0.18 to 0.32 mg C dm^?3 day^?1 (mean 0.25, SE 0.03). The total organic carbon (TOC) of the microbial biofilms ranged from 18.2 to 29.7 mg C dm^?3. Turnover rate ranged from 3.2 to 5.6 year^?1 with a mean of 4.2 year^?1. 4. At the hyporheic site very close to the river, respiration did not significantly increase when samples were supplemented with labile carbon. Respiration increased with increasing DOC addition at hyporheic sites more distant from the river, suggesting a carbon‐limitation gradient within the hyporheic zone. Microbes at the phreatic site did not respond to increasing DOC addition, suggesting that the phreatic biofilm is adapted to low carbon availability. 5. Comparing the volume of the alluvial aquifer (about 0.7 km³) to that of the river benthic sediments (to 0.25 m depth, which amounts to about 1.6 × 10^?4 km³) within the Flathead Valley, leads to the conclusion that interstitial microbial productivity is orders of magnitude greater than benthic productivity. Alluvial aquifers are often voluminous and microbial production is an enormous component of ecosystem production in rivers such as the Flathead.     

Ethyl tert-butyl ether (ETBE) biodegradation by a syntrophic association of Rhodococcus sp. IFP 2042 and Bradyrhizobium sp. IFP 2049 isolated from a polluted aquifer

Ethyl tert-butyl ether (ETBE) enrichment was obtained by adding contaminated groundwater to a mineral medium containing ETBE as the sole carbon and energy source. ETBE was completely degraded to biomass and CO₂ with a transient production of tert-butanol (TBA) and a final biomass yield of 0.37?±?0.08 mg biomass (dry weight).mg^?1 ETBE. Two bacterial strains, IFP 2042 and IFP 2049, were isolated from the enrichment, and their 16S rRNA genes (rrs) were similar to Rhodococcus sp. (99 % similarity to Rhodococcus erythropolis) and Bradyrhizobium sp. (99 % similarity to Bradyrhizobium japonicum), respectively. Rhodococcus sp. IFP 2042 degraded ETBE to TBA, and Bradyrhizobium sp. IFP 2049 degraded TBA to biomass and CO₂. A mixed culture of IFP 2042 and IFP 2049 degraded ETBE to CO₂ with a biomass yield similar to the original ETBE enrichment (0.31?±?0.02 mg?biomass.mg^?1 ETBE). Among the genes previously described to be involved in ETBE, MTBE, and TBA degradation, only alkB was detected in Rhodococcus sp. IFP 2042 by PCR, and none were detected in Bradyrhizobium sp. IFP 2049.     

Kinetic Modeling for Simultaneous Organic Carbon Oxidation,Nitrification, and Denitrification of Abattoir Wastewater in Sequencing Batch Reactor

A laboratory-scale study was conducted in a 20.0-L sequencing batch reactor (SBR) to explore the feasibility of simultaneous removal of organic carbon and nitrogen from abattoir wastewater. The reactor was operated under three different combinations of aerobic-anoxic sequence, viz., (4+4), (5+3), and (5+4) h of total react period, with influent soluble chemical oxygen demand (SCOD) and ammonia nitrogen (NH₄⁺-N) level of 2200 ± 50 and 125 ± 5 mg L^?1, respectively. In (5+4) h cycle, a maximum 90.27% of ammonia reduction corresponding to initial NH₄⁺-N value of 122.25 mg L^?1 and 91.36% of organic carbon removal corresponding to initial SCOD value of 2215.25 mg L^?1 have been achieved, respectively. The biokinetic parameters such as yield coefficient (Y), endogenous decay constant (k_d), and half-velocity constant (K_s) were also determined to improve the design and operation of package effluent treatment plants comprising SBR units. The specific denitrification rate (q_DN) during anoxic condition was estimated as 6.135 mg N/g mixed liquor volatile suspended solid (MLVSS)·h on 4-h average contact period. The value of Y, k_d and K_s for carbon oxidation and nitrification were found to be in the range of 0.6225–0.6952 mg VSS/mg SCOD, 0.0481–0.0588 day^?1, and 306.56–320.51 mg L^?1, and 0.2461–0.2541 mg VSS/mg NH₄⁺-N, 0.0324–0.0565 day^?1, and 38.28–50.08 mg L^?1, respectively, for different combinations of react periods.     

The role of hydrodynamic sorting on the accumulation and distribution of organic carbon in an impoundment: Englebright Lake,California, USA

The global proliferation of dams is one of the most significant anthropogenic impacts on the environment, resulting in the trapping of massive loads of sediment and nutrients in impoundments. Few studies, however, have examined these impounded sediments to understand patterns of organic carbon (OC) accumulation and the effects of watershed processes on carbon delivery. This study measured total organic carbon (TOC) and stable isotopes of carbon and nitrogen (δ¹³C and δ¹⁵N) in Englebright Lake, CA to relate changes in OC sources and TOC accumulation to natural and anthropogenic events in the watershed and to depositional processes in the lake. Englebright Lake is a representative system for impoundments in small, mountainous rivers, and anthropogenic disturbances in the watershed caused high sediment accumulation rates in the lake. Throughout its 60-year history, 0.35 Tg OC has been trapped behind Englebright Dam and δ¹³C signatures indicate that more than 50% of the OC in Englebright Lake was derived from terrigenous sources. TOC content ranged from 0.03 to 30.24% of dry weight, and differed across depositional regimes; TOC content in topset deposits (0.35 ± 0.58%) was less than in foreset (2.64 ± 5.95%) and bottomset (1.51 ± 1.41%) deposits (p < 0.001) and TOC accumulation associated with flood events was higher (up to 231 kg_OC m^?2 year^?1) than during non-event periods (0.2 to 39 kg_OC m^?2 year^?1). TOC accumulation rates in Englebright Lake were up to an order of magnitude higher than previous estimates of OC burial in California impoundments. As the number and size of dams continues to expand worldwide, the storage of TOC in impoundments will likely add to the growing number of anthropogenic modifications to the global carbon cycle.     

Effects of dissolved organic matter from sewage sludge on the atrazine sorption by soils

The effects of dissolved organic matter (DOM), water soluble organic matter derived from sewage sludge, on the sorption of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-trazine) by soils were studied using a batch equilibrium technique. Six paddy soils, chosen so as to have different organic carbon contents, were experimented in this investigation. Atrazine sorption isotherms on soils were described by the linear equation, and the distribution coefficients without DOM (K_d) or with DOM (K_d ^*) were obtained. Generally, the values of K_d ^*/K_d initially increased and decreased thereafter with increasing DOM concentrations of 0–60 mg DOC · L^?1 in soil-solution system form. Critical concentrations of DOM (DOM_np) were obtained where the value of K_d ^* was equal to K_d. The presence of DOM with concentrations lower than DOM_np promoted atrazine sorption on soils (K_d ^* > K_d), whereas the presence of DOM with concentrations higher than DOM_np tended to inhibit atrazine sorption (K_d ^* < K_d). Interestingly, DOM_np for tested soils was negatively correlated to the soil organic carbon content, and the maximum of K_d ^*/K_d (i.e.K _max) correlated positively with the maximum of DOM sorption on soil (X_max). Further investigations showed that the presence of hydrophobic fraction of DOM evidently promoted the atrazine sorption on soils, whereas the presence of hydrophilic DOM fraction obviously tended to inhibit the atrazine sorption. Interactions of soil surfaces with DOM and its fractions were suggested to be the major processes determining atrazine sorption on soils. The results of this work provide a reference to the agricultural use of organic amendment such as sewage sludge for improving the availability of atrazine in soils.     

PREDICTING THE KINETICS OF DISSOLVED INORGANIC CARBON LIMITED GROWTH FROM THE SHORT-TERM KINETICS OF PHOTOSYNTHESIS IN SYNECHOCOCCUS LEOPOLIENSIS (CYANOPHYTA)1

The blue-green alga (Cyanobacterium) Synechococcus leopoliensis (Racib.) Komarek was grown in dissolved inorganic carbon [DIC]-limited chemostats over the entire range of growth rates. At each growth rate, the kinetics of photosynthesis with respect to [DIC] and the maximal rate of photosynthesis (P_max) were determined. The half-saturation constant for [DIC]-limited photosynthesis (K_1/2^DIC) for cells growing below 1.7 d^?1 was constant (4.7 μM) whereas for growth rates between 1.7 d^?1 and 2.1 d^?1 (μ_max) the kinetics of photosynthesis were multiphasic with an apparent K_1/2^DIC between 1.5–2.0 mM. P_max increased in a linear fashion with growth rate for growth rates below 1.7 d^?1. No trend in P_max was apparent for growth rates greater than 1.7 d^?1. These kinetic parameters were used to predict a growth rate versus [DIC] relationship. Results show that the Monod relationship is a physiologically valid expression of growth as a function of [DIC] provided (K_1/2^DIC) remains constant. The major change in (K_1/2^DIC) as μ approaches μ_max results in the conclusion that two separate and distinct Monod equations must be used to describe growth as a function of DIC over the entire growth range. These results point to a major discontinuity in the μ vs. [DIC] curve at 1.7 d^?1 which corresponds to the change from high to low affinity photosynthetic kinetics. We believe these results account for the previously described deficiencies of the Monod equation in describing [DIC]-limited algal growth.     

Biodegradation of methyl <Emphasis Type="Italic">tert</Emphasis>-butyl ether by cold-adapted mixed and pure bacterial cultures

An aerobic mixed bacterial culture (CL-EMC-1) capable of utilizing methyl tert-butyl ether (MTBE) as the sole source of carbon and energy with a growth temperature range of 3 to 30°C and optimum of 18 to 22°C was enriched from activated sludge. Transient accumulation of tert-butanol (TBA) occurred during utilization of MTBE at temperatures from 3°C to 14°C, but TBA did not accumulate above 18°C. The culture utilized MTBE at a concentration of up to 1.5 g l⁻¹ and TBA of up to 7 g l⁻¹. The culture grew on MTBE at a pH range of 5 to 9, with an optimum pH of 6.5 to 7.1. The specific growth rate of the CL-EMC-1 culture on 0.1 g l⁻¹ of MTBE at 22°C and pH 7.1 was 0.012 h⁻¹, and the growth yield was 0.64 g (dry weight) g⁻¹. A new MTBE-utilizing bacterium, Variovorax paradoxus strain CL-8, isolated from the mixed culture utilized MTBE, TBA, 2-hydroxy isobutyrate, lactate, methacrylate, and acetate as sole sources of carbon and energy but not 2-propanol, acetone, methanol, formaldehyde, or formate. Two other isolates, Hyphomicrobium facilis strain CL-2 and Methylobacterium extorquens strain CL-4, isolated from the mixed culture were able to grow on C₁ compounds. The combined consortium could thus utilize all of the carbon of MTBE.     

Sorption of Glyphosate on Soil Components: The Roles of Metal Oxides and Organic Materials

Predicting the behavior, fate, and transport potential of a herbicide in any soil involves understanding the sorption characteristics. The sorption characteristics of glyphosate (GPS) on soil and their main components were investigated, indicating that the mineral phase is more important than the organic carbon in adsorption of GPS. Sorption isotherms were determined from each component using the batch equilibrium method at various concentrations (5, 10, 15, 20, 25, and 30 mg L^?1) and sorption affinity of GPS was approximated by the Freundlich equation. The sorption strength K _f [mg kg^?1 (L mg^?1)^?n] across the various components ranged from 2.1–134.9 while the organic carbon-normalized Freundlich sorption capacity values, K _foc, ranged from 1.28–3.53 mg kg^?1-OC/(mg L^?1)ⁿ. Infrared Fourier transform spectroscopy (FTIR) of the components showed significant structural differences. The results suggest that the presence of the oxides and hydroxides iron, in particular in soil solutions, enhanced GPS adsorption. They also suggest that reduction in OC% due to various treatments may enhance the remobilization of GPS into the aqueous phase (i.e., groundwater), though at different rates. Comparatively, contribution of surface area to the adsorption of GPS on the various components proved more significant than contents of organic carbon.     

Characterization of the Initial Reactions during the Cometabolic Oxidation of Methyl tert-Butyl Ether by Propane-Grown Mycobacterium vaccae JOB5

The initial reactions in the cometabolic oxidation of the gasoline oxygenate, methyl tert-butyl ether (MTBE), by Mycobacterium vaccae JOB5 have been characterized. Two products, tert-butyl formate (TBF) and tert-butyl alcohol (TBA), rapidly accumulated extracellularly when propane-grown cells were incubated with MTBE. Lower rates of TBF and TBA production from MTBE were also observed with cells grown on 1- or 2-propanol, while neither product was generated from MTBE by cells grown on casein-yeast extract-dextrose broth. Kinetic studies with propane-grown cells demonstrated that TBF is the dominant (≥80%) initial product of MTBE oxidation and that TBA accumulates from further biotic and abiotic hydrolysis of TBF. Our results suggest that the biotic hydrolysis of TBF is catalyzed by a heat-stable esterase with activity toward several other tert-butyl esters. Propane-grown cells also oxidized TBA, but no further oxidation products were detected. Like the oxidation of MTBE, TBA oxidation was fully inhibited by acetylene, an inactivator of short-chain alkane monooxygenase in M. vaccae JOB5. Oxidation of both MTBE and TBA was also inhibited by propane (K_i = 3.3 to 4.4 μM). Values for K_s of 1.36 and 1.18 mM and for V_max of 24.4 and 10.4 nmol min⁻¹ mg of protein⁻¹ were derived for MTBE and TBA, respectively. We conclude that the initial steps in the pathway of MTBE oxidation by M. vaccae JOB5 involve two reactions catalyzed by the same monooxygenase (MTBE and TBA oxidation) that are temporally separated by an esterase-catalyzed hydrolysis of TBF to TBA. These results that suggest the initial reactions in MTBE oxidation by M. vaccae JOB5 are the same as those that we have previously characterized in gaseous alkane-utilizing fungi.     

Temperature effect on tert-butyl alcohol (TBA) biodegradation kinetics in hyporheic zone soils

Background  

Remediation of tert-butyl alcohol (TBA) in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-butyl formate (TBF). The effect of temperature on TBA biodegradation has not been not been published in the literature.     

The hyporheic zone as a source of dissolved organic carbon and carbon gases to a temperate forested stream

The objective of this study was to examine chemical changes in porewaters that occur over small scales (cm) as groundwater flows through the hyporheic zone and discharges to a stream in a temperate forest of northern Wisconsin. Hyporheic-zone porewaters were sampled at discrete depths of 2, 10, 15, 61, and 183 cm at three study sites in the study basin. Chemical profiles of dissolved organic carbon (DOC), CO₂, CH₄, and pH show dramatic changes between 61 cm sediment depth and the water-sediment interface. Unless discrete samples at small depth intervals are taken, these chemical profiles are not accounted for. Similar trends were observed at the three study locations, despite each site having very different hydraulic-flow regimes. Increases in DOC concentration by an order of magnitude from 61 to 15 cm depth with a corresponding decrease in pH and rapid decreases in the molecular weight of the DOC suggest that aliphatic compounds (likely organic acids) are being generated in the hyporheic zone. Estimated efflux rates of DOC, CO₂, and CH₄ to the stream are 6.2, 0.79, 0.13 moles m² d^-1, respectively, with the vast majority of these materials produced in the hyporheic zone. Very little of these materials are accounted for by sampling stream water, suggesting rapid uptake and/or volatilization.     

Modeling the Kinetics of Contaminant Biodegradation by a Mixed Microbial Consortium Based on Carbon Mass Balance

The fate of contaminant carbon was monitored during aerobic biodegradation in the presence of a mixed indigenous microbial consortium in order to calibrate a microbial-growth-based biokinetic model. The methodology simultaneously monitored mineralization, substrate depletion and microbial population evolution in biomass extract spiked with¹⁴C-labeled hexadecane. Hexadecane depletion and hexadecane-degrader population were monitored using sacrificed microcosms by centrifuging the extract so that the supernatant and the residue contained residual hexadecane and microbial population, respectively. This methodology allowed verification of the carbon mass balance (average¹⁴C-carbon recovery of 90.33 ± 1.62% for biotic microcosms) and calibration of a biokinetic model. Four biokinetic parameters and three yield coefficients were identified (Haldane kinetic parameters:μ_S = 1.3639 d^-1, K_s = 0.4295 mg-C, KI = 6.6457 mg-C; decay kinetic parameter:μ_d = 1.3.10² d^-1; substrate/biomass, carbon dioxide/ biomass during growth and carbon dioxide/biomass during decay yield coefficients: Y_s = 1.5948 mg-C/mg-C, Y_P ^g = 0.4554 mg-C/mg-C, Y_P ^d = 1.3263 mg-C/mg-C) and compared with the literature data. The methodology can facilitate the identification of biodegradation models by decoupling the intrinsic ability of microorganisms to degrade contaminant from restrictions imposed by limiting conditions.     

Cometabolism of methyl tert-butyl ether (MTBE) with alkanes

The release of methyl tert-butyl ether (MTBE) to the environment, mainly from damaged gasoline underground storage tanks or distribution systems spills, has provoked extended groundwater pollution. Biological treatments are, in general, a good alternative for bioremediation of polluted sites; however, MTBE elimination from environment has constituted a challenge because of its chemical structure and physicochemical properties. The combination of a stable ether link and the branched moiety hinder biodegradation. Initial studies found MTBE to be highly recalcitrant but, in the last decade, reports of its biodegradation have been published first under aerobic conditions and just recently under anaerobic conditions. Microbial MTBE degradation is characterized by bacteria having low growth rates (0.35 day⁻¹) and biomass yields (average value 0.24 g biomass/g MTBE). Alternatively, cometabolism (defined as the transformation of a non-growth substrate in the obligate presence of a growth substrate), has been considered since it uncouples biodegradation of the contaminant from growth, reducing the long adaptation and propagation period. This period has been reported to be of several months in systems where it is degraded as sole carbon source. Cometabolic degradation rates are between 0.3 and 61 nmol/min/mg protein (in the same range of direct aerobic metabolism). However, a major concern in MTBE cometabolism is that the accumulation of tert-butyl alcohol (TBA) may, under certain cases, result in an incomplete site cleanup. This paper reviews in detail the implicated enzymes and field treatments for the cometabolism of MTBE degradation with alkanes as growth substrates.     

CO2 Supersaturation and Net Heterotrophy in a Tropical Estuary (Cochin, India): Influence of Anthropogenic Effect

Carbon biogeochemistry of a tropical ecosystem (The Cochin Estuary, India) undergoing increased human intervention was studied during February (premonsoon), April (early monsoon) and September (monsoon) 2005. The Cochin estuary sustains high levels of pCO₂ (up to 6000 μatm) and CO₂ effluxes (up to 274 mmolC m^?2 d^?1) especially during monsoon. A first-order estimate of the carbon mass balance shows that net production of dissolved inorganic carbon is an order of magnitude higher than the net loss of dissolved and particulate organic carbon from the estuary. This imbalance is attributed to the organic inputs to the estuary through anthropogenic supplies. The bacteria-mediated mineralization of organic matter is mainly responsible for the build-up of pCO₂ and increased CO₂ emission to the atmosphere indicating heterotrophy. The linear correlation between excess CO₂ and apparent oxygen utilization indicates respiration as the chief mechanism for CO₂ supersaturation. An increase in the net negative ecosystem production (–ve NEP) between premonsoon (?136 mmolC m^?2 d^?1 or ?376 MgC d^?1) and monsoon (?541 mmolC m^?2 d^?1 or ?1500 MgC d^?1) is supported by a corresponding increase in O₂ influxes from 17 mmol O₂ m^?2 d^?1 (126 MgC d^?1) to ?128 mmol O₂ m^?2 d^?1 (?946 MgC d^?1) and CO₂ emissions from 65 mmolC m^?2 d^?1 (180 MgC d^?1) to 267 mmolC m^?2 d^?1 (740 MgC d^?1). There is a significant north-south gradient in metabolic rates and CO₂ fluxes attributable to the varying flow patterns and anthropogenic inputs into the estuary. The study reveals that the Cochin estuary, a previously autotrophic (CO₂ sink) system, has been transformed to a heterotrophic (CO₂ source) system following rapid urbanization and industrialization. Moreover, the export fluxes from the Cochin estuary appear to be quite important in sustaining net heterotrophy in the southeastern Arabian Sea.     

Evaluating the Adsorption Potential of Alachlor and Its Subsequent Removal from Soils via Activated Carbon

Alachlor, a globally used aniline herbicide, has great agronomic interest for controlling the development of broadleaved weeds and grasses. This research aspires to evaluate the sorption attributes of Alachlor through batch equilibrium method and its successive removal through biomass based activated carbon prepared from Sawdust (Cedrus deodara). Six soil samples were collected from selected regions of Pakistan to assess the adsorption and removal phenomena. Adsorption capacity for Alachlor varied in soils depending upon their physicochemical properties. Adsorption coefficient (K_d) values ranged from 12 to 31 µg ml^?1 with the highest K_d value observed in soil sample with highest organic content (1.4%) and least pH (5.62). The Gibbs free energy values ranged from ?17 to ?20 kJ mol^?1 proposing physio-sorption and exothermic interaction with soils. Values of R² (0.96–0.99) exhibited the best fit to linear adsorption model. Adsorption coefficient displayed a negative correlation (r = ?0.97) with soil pH and positive correlation with organic matter (r = 0.87). The effect of contact time and pesticide concentration on the removal efficiency by activated carbon was investigated. The highest removal percentages observed through activated carbon were 66% and 64% at concentrations of 5 and 7.5 ppm respectively. Activated carbon from sawdust (Cedrus deodara) was investigated as a suitable adsorbent for the removal of Alachor from selected soils. Biomass based activated carbon can prove to be an effective and a sustainable mean to remove pesticides from soil.     

Effect of Benzene, Toluene, Ethylbenzene, and p-Xylene (BTEX) Mixture on Biodegradation of Methyl tert-Butyl Ether (MTBE) and tert-Butyl Alcohol (TBA) by Pure Culture UC1

The effect of a BTEX mixture on the biodegradation of methyl tert-butyl ether (MTBE) and its degradation intermediate, tert-butyl alcohol (TBA) was investigated in the pure bacterial culture UC1, which has been identified to be a strain of the known MTBE-degrader PM1 based on greater than 99% 16S rDNA similarity. Several degradation studies were carried out on UC1 at three initial concentration levels of MTBE or TBA: 6-7; 15-17; and 40-45 mg/l, both with and without BTEX present cumulatively at about half of the MTBE or TBA molar mass in the system. The BTEX mixture was observed not to affect either the rate or the degradation lag period of MTBE or TBA degradation, except that the TBA degradation rate actually increased when BTEX was present initially in the highest concentration studies. When serving as the sole substrate, the MTBE degradation rate ranged from 48 +/- 1.2 to 200 +/- 7.0 mg(MTBE)/g(dw) h, and the TBA degradation rate from 140 +/- 18 to 530 +/- 70 mg(TBA)/g(dw) h. When present with BTEX, MTBE and TBA rates ranged from 46 +/- 2.2 to 210 +/- 14 and 170 +/- 28 to 780 +/- 43 mg(TBA)/g(dw) h, respectively. In studies where varying concentrations of TBA were present with 5 mg/l MTBE, both compounds were degraded simultaneously with no obvious preference for either substrate. In the highest concentration study of TBA with 5 mg/l MTBE, BTEX was also observed to increase the ultimate rate of TBA degradation. In addition to exploring the affect of BTEX, this study also provides general insight into the metabolism of MTBE and TBA by pure culture UC1.     

Importance of transient storage zones for ammonium and phosphate retention in a sandy-bottom Mediterranean stream

1. The ability of hyporheic sediments to exchange water and retain ammonium and phosphate in the Riera Major stream ,North-East Spain, under different discharge conditions was measured by conducting short-term nutrient and chloride additions. 2. The mean exchange coefficients from free-flowing water to the storage zone (k₁) and vice versa (k₂) were 0.82 × 10–4 s^??1 and 7 × 10^??3 s^??1, respectively. The ratio of storage zone cross-sectional area to stream cross-sectional area (A_S/A) averaged 2.8 × 10–2 and was negatively correlated with discharge (r = –0.85, d.f. = 13, P < 0.001). 3. The percentage of hyporheic zone water which came from surface water varied as a function of discharge and hyporheic depth, ranging between 33% and 95% at 25 cm depth, and between 78% and 100% at 10 cm depth. 4. The nutrient retention efficiency in the hyporheic zone at 10 cm depth measured as uptake length (S_wh) was less than 3.3 cm for ammonium and 37 cm for phosphate. Higher nutrient retentions were measured in the sediments at 10 cm depth than at 25 cm, indicating that near-surface sediments were involved more actively in phosphate retention than the deeper hyporheic sediments. The lack of ammonium at any depth of the hyporheic zone showed that ammonium was very rapidly taken up in the surfacial sediments.