Degree of Sulfate‐Reducing Activities on COD Removal in Various Reactor Configurations in Anaerobic Glucose and Acetate‐fed Reactors

Sulfate‐reduction data from various anaerobic reactor configurations, e. g., upflow anaerobic sludge blanket reactor (UASBR), completely stirred tank reactor (CSTR), and batch reactor (BR) with synthetic wastewaters, having glucose and acetate as the substrates and different levels of sulfate, were evaluated to determine the level of sulfate‐reducing activity by sulfate‐reducing bacteria coupled to organic matter removal. Anaerobic reactors were observed for the degree of competition between sulfate‐reducing sulfidogens and methane producing bacteria during the degradation of glucose and acetate. Low sulfate‐reducing activity was obtained with a maximum of 20% of organic matter degradation with glucose‐fed upflow anaerobic sludge bed reactors (UASBRs), while a minimum of 2% was observed with acetate‐fed batch reactors. The highest sulfate removal performance (72–89%) was obtained from glucose fed‐UASB reactors, with the best results observed with increasing COD/SO₄ ratios. UASB reactors produced the highest level of sulfidogenic activity, with the highest sulfate removal and without a performance loss. Hence, this was shown to be the optimum reactor configuration. Dissolved sulfide produced as a result of sulfate reduction reached 325 mg/L and 390 mg/L in CST and UASB reactors, respectively, and these levels were tolerated. The sulfate removal rate was higher at lower COD/SO₄ ratios, but the degree of sulfate removal improved with increasing COD/SO₄ ratios.     

Stochastic modeling applications for the prediction of COD removal efficiency of UASB reactors treating diluted real cotton textile wastewater

A three-layer Artificial Neural Network (ANN) model (9:12:1) for the prediction of Chemical Oxygen Demand Removal Efficiency (CODRE) of Upflow Anaerobic Sludge Blanket (UASB) reactors treating real cotton textile wastewater diluted with domestic wastewater was presented. To validate the proposed method, an experimental study was carried out in three lab-scale UASB reactors to investigate the treatment efficiency on total COD reduction. The reactors were operated for 80 days at mesophilic conditions (36–37.5°C) in a temperature-controlled water bath with two hydraulic retention times (HRT) of 4.5 and 9.0 days and with organic loading rates (OLR) between 0.072 and 0.602 kg COD/m³/day. Five different dilution ratios of 15, 30, 40, 45 and 60% with domestic wastewater were employed to represent seasonal fluctuations, respectively. The study was undertaken in a pH range of 6.20–8.06 and an alkalinity range of 1,350–1,855 mg/l CaCO₃. The concentrations of volatile fatty acids (VFA) and total suspended solids (TSS) were observed between 420 and 720 mg/l CH₃COOH and 68–338 mg/l, respectively. In the study, a wide range of influent COD concentrations (COD_i) between 651 and 4,044 mg/l in feeding was carried out. CODRE of UASB reactors being output parameter of the conducted anaerobic treatment was estimated by nine input parameters such as HRT, pH, COD_i concentration, operating temperature, alkalinity, VFA concentration, dilution ratio (DR), OLR, and TSS concentration. After backpropagation (BP) training combined with principal component analysis (PCA), the ANN model predicted CODRE values based on experimental data and all the predictions were proven to be satisfactory with a correlation coefficient of about 0.8245. In the ANN study, the Levenberg-Marquardt Algorithm (LMA) was found as the best of 11 BP algorithms. In addition to determination of the optimal ANN structure, a linear-nonlinear study was also employed to investigate the effects of input variables on CODRE values in this study. Both ANN outputs and linear-nonlinear study results were compared and advantages and further developments were evaluated.     

Festkontaktierte potentiometrische Elektroden für Sulfatbestimmungen in wässrigen Lösungen

Solid‐contacted Potentiometric Electrodes for Measurements of Sulfate Ions in Aqueous Solutions A solid‐contact electrode for potentiometric measurement of sulfate ions in aqueous solutions was developed and examined. The electrode is based on a PVC membrane which contains the ionophore 3‐decyl‐1,5,8‐triazacyclodecan‐2,4‐dione (DTADD). Instead of the usual inner fluid junction, a polypyrrole layer applied on the inner side of the PVC membrane was employed as inner solid contact. The performance of this electrode was compared to solid‐state sulfate‐selective electrodes with the ionophore α,α′‐bis(N′‐phenylthioureylene)‐m‐xylene (BTH) and to electrodes in the coated‐wire configuration. For the parameters sensitivity, selectivity, and long‐term stability, electrodes with the DTADD ionophore show improved properties. In the sulfate concentration range of 5·10^–5...10^–2 mol L^–1 the slope of the response is –(26.8 ± 0.5) mV/decade. The new solid contact sulfate electrodes showed a very low drift of the electrode potential within a period of 150 days when the electrode was stored in 10^–2 M Na₂SO₄. In Na2SO4 solutions of the pH range of 4...9 the electrode potentials were constant. The 95% response time was about 10 s when the sulfate concentration was changed from 10^–4 mol L^–1 to 10^–3 mol L^–1. The selectivity with DTADD ionophore relating to the nitrate ions is higher than the selectivity with BTH. Improvements are also made in comparison with sulfate‐selective electrodes described in the literature which contain other ionophores with fluid inner reference electrolytes.     

Environmental Factors Associated With Natural Methane Occurrence in the Appalachian Basin

The recent boom in shale gas development in the Marcellus Shale has increased interest in the methods to distinguish between naturally occurring methane in groundwater and stray methane associated with drilling and production operations. This study evaluates the relationship between natural methane occurrence and three principal environmental factors (groundwater redox state, water type, and topography) using two pre‐drill datasets of 132 samples from western Pennsylvania, Ohio, and West Virginia and 1417 samples from northeastern Pennsylvania. Higher natural methane concentrations in residential wells are strongly associated with reducing conditions characterized by low nitrate and low sulfate ([NO₃^?] < 0.5 mg/L; [SO₄^2?] < 2.5 mg/L). However, no significant relationship exists between methane and iron [Fe(II)], which is traditionally considered an indicator of conditions that have progressed through iron reduction. As shown in previous studies, water type is significantly correlated with natural methane concentrations, where sodium (Na) ‐rich waters exhibit significantly higher (p<0.001) natural methane concentrations than calcium (Ca)‐rich waters. For water wells exhibiting Na‐rich waters and/or low nitrate and low sulfate conditions, valley locations are associated with higher methane concentrations than upland topography. Consequently, we identify three factors (“Low NO₃^? & SO₄^2?” redox condition, Na‐rich water type, and valley location), which, in combination, offer strong predictive power regarding the natural occurrence of high methane concentrations. Samples exhibiting these three factors have a median methane concentration of 10,000 µg/L. These heuristic relationships may facilitate the design of pre‐drill monitoring programs and the subsequent evaluation of post‐drill monitoring results to help distinguish between naturally occurring methane and methane originating from anthropogenic sources or migration pathways.     

Enhancing the Performance of Anaerobic Digestion of Dairy Manure through Phase‐Separation

Anaerobic digestion (AD) is an effective way to convert animal manures into profitable by‐products while simultaneously reducing the pollution of water, air, and soil caused by these wastes. Conventional high‐rate anaerobic reactors cannot effectively process animal manures with high solids‐containing wastes. The two‐phase configuration for AD has several advantages over conventional one‐phase processes, e. g., increased stability of the process, smaller size and cost efficient process configurations. In the present study, the experiments were carried out in a two‐phase system composed of an acidogenic reactor and a methanogenic reactor, and in a one‐phase system composed of only a methanogenic reactor. The reactors were operated as unmixed (without an external mixing aid), unsophisticated, and daily‐fed mode. It was found that the two‐phase configuration was more efficient than the one‐phase system. The biogas production in the two‐phase system at a hydraulic retention time (HRT) of 8.6 days (only methanogenic phase) was calculated to be 42% higher at an organic loading rate (OLR) of 3.5 g VS/L·day than that of the one‐phase with a HRT of 20 days. This translates into significant performance improvement and reduced volume requirement. This finding represents a further step in the achievement of wider use of simple anaerobic reactor configurations for waste treatment in rural areas.     

Evaluation of a Novel Control Method on Biofilm Parameters in an Aerated Submerged Fixed‐bed Biofilm Reactor

One of the critical technological parameter in operation of aerated submerged fixed‐bed biofilm reactor (ASFBBR) is the control over process of biofilm detachment. Both, an excessive growth of biomass with its accumulation in the bioreactor and an exceeded biofilm detachment rate, cause serious operational and technological problems. The studies presented in this paper demonstrate that in an ASFBBR reactor with a PVC bed carrier media, an effective way to maintain a proper shear stress acting on the biofilm and causing its detachment could be an internal recirculation of wastewater instead of backwashing with wastewater or air flushing. In case of polishing of oil‐refinery wastewater with average COD loading rate equal to 9 g COD/(m² day), the minimum value of the hydraulic loading rate in such reactor is 1.9 m³/(m² h), at which there was no excessive growth of biofilms. Despite a significant decrease of the biofilms thickness and amount of biomass in the reactor, there was no significant decline in the efficiency of pollutant removal from oil‐refinery wastewater, which made it possible to obtain the quality of effluent at the outlet of the bioreactor significantly below the water permits and standards.     

Thresholds and relations for soil‐hydraulic and soil‐physical properties as a function of burn severity 4 years after the 2011 Las Conchas Fire,New Mexico,USA

Wildfire effects on soil‐physical and ‐hydraulic properties as a function of burn severity are poorly characterized, especially several years after wildfire. A stratified random sampling approach was used in 2015 to sample seven sites representing a spectrum of remotely sensed burn severity in the area impacted by the 2011 Las Conchas Fire in New Mexico, USA. Replicate samples from each site were analysed in the laboratory. Linear and linear indicator regression were used to assess thresholds in soil‐physical and ‐hydraulic properties and functional relations with remotely sensed burn severity. Significant thresholds were present for initial soil‐water content (θ_i) at 0–6 cm depth between the change in the Normalized Burn Ratio (dNBR) equal to 618–802, for bulk density (ρ_b) at 3–6 cm between dNBR equal to 416–533, for gravel fraction at 0–1 cm between dNBR equal to 416–533, for fines (the silt + clay fraction) at 0–1 cm for dNBR equal to 416–533, and for fines at 3–6 cm for dNBR equal to 293–416. Significant linear relations with dNBR were present between ρ_b at 0–1 cm, loss on ignition (LOI) at 0–1 cm, gravel fraction at 0–1 cm, and the large organic fraction at 1–3 cm. No thresholds or effects on soil‐hydraulic properties of field‐saturated hydraulic conductivity or sorptivity were observed. These results suggest that ρ_b and LOI at 0–1 cm have residual direct impacts from the wildfire heat impulse. The θ_i threshold is most likely from delayed groundcover/vegetation recovery that increases evaporation at the highest burn severity sites. Gravel and silt + clay thresholds at 0–1 cm at the transition to high burn severity suggest surface gravel lag development from hydraulic erosion. Thresholds in ρ_b from 3 to 6 cm and in silt + clay fraction from 3 to 6 cm appear to be the result of soil variability between sites rather than wildfire impacts. This work suggests that gravel‐rich soils may have increased resilience to sustained surface runoff generation and erosion following wildfire, with implications for assessments of postwildfire hydrologic and erosion recovery potential.     

Individual and Synergistic Effects of Metronidazole,Amoxicillin, and Ciprofloxacin on Methane Fermentation with Sewage Sludge

Methane fermentation is widely used to dispose of sewage sludge at wastewater treatment plants (WWTPs), due to production of renewable energy in the form of biogas. Antibiotics present in wastewater may accumulate in a sewage sludge. The aim of the present study is to investigate the impact of three antibiotics from different classes in three different doses on methane production from sewage sludge. For this purpose, metronidazole (MET), amoxicillin (AMO), and ciprofloxacin (CIP) are individually added to anaerobic reactors with sewage sludge collected from municipal WWTP. The antibiotics’ highest concentration (1024 mg kg^?1 of AMO; 512 mg kg^?1 of MET and CIP) lowers methane production and methane content in biogas. MET exerts the most marked effect and lowers methane production to 36.8 ± 3.7 mL CH₄ kg^?1 volatile solids. Tested antibiotics probably inhibit methanogenic archaea, which results in volatile fatty acids (VFAs) accumulation. Addition of MET results in accumulation of many kinds of VFAs with the highest concentration of acetic acid (17.52 ± 1.85 g L^?1). The addition of of AMO results in accumulation of butyric acid only (253.00 ± 15.89 g L^?1). However, addition of CIP results in accumulation of mainly acetic acid (7.58 ± 0.82 g L^?1) and isovaleric acid (2.01 ± 0.41 g L^?1). Next, synergistic effect of these antibiotics in a low concentration of 16 mg kg^?1 of AMO, 8 mg kg^?1 of MET, and 2 mg kg^?1 of CIP is measured in semi‐continuous conditions and causes inbibition of methane production and accumulation of VFAs.     

Effect of SO on 1,1,1‐Trichloroethane Degradation by Fe0 in Aqueous Solution

Sulfate in groundwater has been previously shown to change the reactivity of Fe⁰ in permeable reactive barriers for reducing chlorinated organics. To better understand the effect and mechanism of SO, the degradation of 1,1,1‐trichloroethane (TCA) by Fe⁰ in unbuffered aqueous solutions with and without SO was investigated. In a Fe⁰‐TCA‐H₂O system with initial pH of 2.0 to 10.0, the maximum removal rate of TCA was achieved at the initial pH 6.0 with pseudo‐first‐order constant K_obs 9.0 × 10^?3/min. But in a Fe⁰‐TCA‐Na₂SO₄‐H₂O system, the removal rate of TCA decreased remarkably with a reduction in K_obs to 1.0 × 10^?3/min, and the pH varied from 6.0 to 9.6, indicating an inhibition of TCA dehydrochlorination by SO. Sulfate remarkably inhibited TCA degradation via changing the route of Fe⁰ dissolution. It accelerated the dissolution of Fe⁰ and transformed the intermediate form Fe(OH)_ads to Fe₂(SO₄)_ads, which weakened the affinity between Fe and TCA, and thus depressed the degradation of TCA by Fe⁰.     

Start‐Up Study on Biohydrogen from Palm Oil Mill Effluent in a Pilot‐Scale Reactor

A start‐up study for biohydrogen production from palm oil mill effluent (POME) is carried out in a pilot‐scale up‐flow anaerobic sludge blanket fixed‐film reactor (UASFF). A substrate with a chemical oxygen demand (COD) of 30 g L^?1 is used, starting with molasses solution for 30 days and followed by a 10% v/v increment of POME/molasses ratio. At 100% POME, a hydrogen content of 80%, hydrogen production rate of 36 L H₂ per day, and maximum COD removal of 48.7% are achieved. Bio‐kinetic coefficients of Monod, first‐order, Grau second‐order, and Stover‐Kincannon kinetic models are calculated to describe the performance of the system. The steady‐state data with 100% POME shows that Monod and Stover‐Kincannon models with bio‐kinetic coefficients of half‐velocity constant (K_s) of 6000 mg COD L^?1, microbial decay rate (K_d) of 0.0015 per day, growth yield constant (Y) of 0.786 mg volatile suspended solids (VSS)/mg COD, specific biomass growth rate (μ_max) of 0.568 per day, and substrate consumption rate of (U_max) 3.98 g/L day could be considered as superior models with correlation coefficients (R²) of 0.918 and 0.989, respectively, compared to first‐order and Grau's second‐order models with coefficients of K₁ 1.08 per day, R² 0.739, and K_2s 1.69 per day, a = 7.0 per day, b = 0.847.     

Sulfate Land Application Enhances Biodegradation in a Petroleum Hydrocarbon Smear Zone

Delivery of sulfate to petroleum hydrocarbons (PHCs) source zones and groundwater plumes is desirable to enhance biodegradation rates when treatment has become limited due to depletion of sulfate. Sulfate land application involves spreading sulfate salts on ground surface and allowing their dissolution and infiltration of sulfate into subsurface. The objectives of this pilot-scale investigation were to capture the vertical transport of sulfate beneath an application area, confirm that sulfate reduction was occurring, and explore how the added sulfate affected biodegradation of benzene and toluene. Approximately 4000 kg of gypsum was spread over a 30 m × 30 m study area above a smear zone located approximately 2 m below-ground surface. Precipitation was augmented by two irrigation events. Groundwater samples, collected over 1058 days from multilevel wells and a conventional long-screened monitoring well, were analyzed for benzene, toluene, ethylbenzene, and xylenes (BTEX), sulfate, bromide, dissolved inorganic carbon (DIC) and methane. Compound-specific isotope analyses (CSIA) for benzene and toluene, and isotope analyses of ¹³C-DIC and ³⁴S-SO₄²⁻ were performed. Following application, an increase in sulfate concentration was noted in the smear zone. ³⁴S-SO₄²⁻ enrichment and ¹³C-DIC depletion indicated that sulfate reduction and mineralization of PHCs were enhanced. CSIA results provided unequivocal evidence of anaerobic biodegradation of benzene and toluene. After 1058 days when sulfate was depleted, methane concentrations were about three times greater than baseline conditions suggesting syntrophic benefit of the delivered sulfate. Observations from this investigation support the viability of sulfate land application to enhance biodegradation rates in shallow PHC smear zones.     

Methanogenesis in the sediment of the acidic Lake Caviahue in Argentina

The biogeochemistry of methane in the sediments of Lake Caviahue was examined by geochemical analysis, microbial activity assays and isotopic analysis. The pH in the water column was 2.6 and increased up to a pH of 6 in the deeper sediment pore waters. The carbon isotope composition of CH₄ was between − 65 and − 70‰ which is indicative for the biological origin of the methane. The enrichment factor ε increased from − 46‰ in the upper sediment column to more than − 80 in the deeper sediment section suggesting a transition from acetoclastic methanogenesis to CO₂ reduction with depth. In the most acidic surface layer of the sediment (pH < 4) methanogenesis is inhibited as suggested by a linear CH₄ concentration profile, activity assays and MPN analysis. The CH₄ activity assays and the CH₄ profile indicate that methanogenesis in the sediment of Lake Caviahue was active below 40 cm depth. At that depth the pH was above 4 and sulfate reduction was sulfate limited. Methane was diffusing with a flux of 0.9 mmol m^− 2 d^− 1 to the sediment surface where it was probably oxidized. Methanogenesis contributed little to the sediments carbon budget and had no significant impact on lake water quality. The high biomass content of the sediment, which was probably caused by the last eruption of Copahue Volcano, supported high rates of sulfate reduction which probably raised the pH and created favorable conditions for methanogens in deeper sediment layers.     

Hydraulic properties of peat soils along a bulk density gradient—A meta study

Our understanding of hydraulic properties of peat soils is limited compared with that of mineral substrates. In this study, we aimed to deduce possible alterations of hydraulic properties of peat soils following degradation resulting from peat drainage and aeration. A data set of peat hydraulic properties (188 soil water retention curves [SWRCs], 71 unsaturated hydraulic conductivity curves [UHCs], and 256 saturated hydraulic conductivity [K_s] values) was assembled from the literature; the obtained data originated from peat samples with an organic matter (OM) content ranging from 23 to 97 wt% (weight percent; and according variation in bulk density) representing various degrees of peat degradation. The Mualem‐van Genuchten model was employed to describe the SWRCs and UHCs. The results show that the hydraulic parameters of peat soils vary over a wide range confirming the pronounced diversity of peat. Peat decomposition significantly modifies all hydraulic parameters. A bulk density of approximately 0.2 g cm^?3 was identified as a critical threshold point; above and below this value, macroporosity and hydraulic parameters follow different functions with bulk density. Pedotransfer functions based on physical peat properties (e.g., bulk density and soil depth) separately computed for bog and fen peat have significantly lower mean square errors than functions obtained from the complete data set, which indicates that not only the status of peat decomposition but also the peat‐forming plants have a large effect on hydraulic properties. The SWRCs of samples with a bulk density of less than 0.2 g cm^?3 could be grouped into two to five classes for each peat type (botanical composition). The remaining SWRCs originating from samples with a bulk density of larger than 0.2 g cm^?3 could be classified into one group. The Mualem‐van Genuchten parameter values of α can be used to estimate K_s if no K_s data are available. In conclusion, the derived pedotransfer functions provide a solid instrument to derive hydraulic parameter values from easily measurable quantities; however, additional research is required to reduce uncertainty.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Land Application of Sulfate Salts for Enhanced Natural Attenuation of Benzene in Groundwater: A Case Study

Sulfate reducing conditions are widely observed in groundwater plumes associated with petroleum hydrocarbon releases. This leads to sulfate depletion in groundwater which can limit biodegradation of hydrocarbons (usually benzene, toluene, ethylbenzene, xylenes [BTEX] compounds) and can therefore result in extended timeframes to achieve groundwater cleanup objectives by monitored natural attenuation. Under these conditions, sulfate addition to the subsurface can potentially enhance BTEX biodegradation and facilitate enhanced natural attenuation. However, a delivery approach that enables effective contact with the hydrocarbons and is able to sustain elevated and uniform sulfate concentrations in groundwater remains a key challenge. In this case study, sulfate addition to a groundwater plume containing predominantly benzene by land application of agricultural gypsum and Epsom salt is described. Over 4 years of groundwater monitoring data from key wells subjected to pilot‐scale and site‐wide land application events are presented. These are compared to data from pilot testing employing liquid Epsom salt injections as an alternate sulfate delivery approach. Sulfate land application, sulfate retention within the vadose zone, and periodic infiltration following ongoing precipitation events resulted in elevated sulfate concentrations (>150 mg/L) in groundwater that were sustained over 12 months between application events and stimulated benzene biodegradation as indicated by declines in dissolved benzene concentration, and compound‐specific isotope analysis data for carbon in benzene. Long‐term groundwater benzene concentration reductions were achieved in spite of periodic rebounds resulting from water table fluctuations across the smear zone. Land application of gypsum is a potentially cost‐effective sulfate delivery approach at sites with open, unpaved surfaces, relatively permeable geology, and shallow hydrocarbon impacts. However, more research is needed to understand the fate and persistence of sulfate and to improve the likelihood of success and effectiveness of this delivery approach.     

Degradation and Detoxification of Chlorophenols in Continuous‐Flow Fixed‐Bed Aerobic Reactors

An indigenous bacterial strain of Delftia sp. capable of degrading 2,4‐dicholorophenol and an indigenous bacterial community that degrades 2,4,6‐trichlorophenol (TCP) were employed to inoculate continuous down‐flow fixed‐bed reactors. Continuous‐reactors were constructed from PVC employing hollow PVC cylinders as support material. Synthetic wastewater was prepared by dissolving the corresponding chlorophenol in non‐sterile groundwater. Biodegradation was evaluated by spectrophotometry, chloride release, GC, and microbial growth. Detoxification was evaluated by using Daphnia magna as test organism. Delftia sp. was able to remove an average of 95.6% of DCP. Efficiency in terms of chemical oxygen demand (COD) was of 88.9%. The indigenous bacterial community that degrades TCP reached an average efficiency of 96.5 and 91.6% in terms of compound and COD removal, respectively. In both cases stoichiometric removal of chloride and detoxification was achieved. When synthetic wastewater feed was cut off for 7 days, both reactors showed a fast recovery after inflow restarting, reaching average outlet concentration values within 36 h. The promising behavior of the microorganisms and the low cost of the reactors tested allow us to suggest their possible application to remediation processes.     

Potential use of mangroves as constructed wetland for municipal sewage treatment in Futian,Shenzhen, China

A pilot-scale mangrove wetland was constructed in Futian, Shenzhen for municipal sewage treatment. Three identical belts (length: 33 m, width: 3 m, depth: 0.5 m) were filled with stone (bottom), gravel and mangrove sand (surface). Seedlings of two native mangrove species (Kandelia candel, Aegiceras corniculatum) and one exotic species (Sonneratia caseolaris) were transplanted to the belts with one species for each belt. The hydraulic loading was 5 m³ d⁻¹ and hydraulic retention time 3 d. High levels of removal of COD, BOD₅, TN, TP and NH₃–N were obtained. The treatment efficiency of S. caseolaris and A. corniculatum was higher than that of K. candel. Faster plant growth was obtained for S. caseolaris. The substrate in the S. caseolaris belt also showed higher enzyme activities including dehydrogenase, cellulase, phosphatase, urease and β-glucosidase. The removal rates of organic matter and nutrients were positively correlated with plant growth. The results indicated that mangroves could be used in a constructed wetland for municipal sewage treatment, providing post-treatment to remove coliforms was also included.     

Nutrients,irradiance, and mixing as factors regulating primary production in coastal waters impacted by the Mississippi River plume

Relationships among primary production, chlorophyll, nutrients, irradiance and mixing processes were examined along the salinity gradient in the Mississippi River outflow region. A series of six cruises were conducted during 1988–1992 at various times of year and stages of river discharge. Maximum values of biomass and primary production were typically observed at intermediate salinities and coincided with non-conservative decreases in nutrients along the salinity gradient. Highest values of productivity (>10 gC m⁻² d⁻¹) and biomass (>30 mg chlorophyll a m⁻³) were observed in April 1988, July–August 1990 and April–May 1992; values were lower in March and September 1991. Rates of primary production were apparently constrained by low irradiance and mixing in the more turbid, low salinity regions of the plume, and by nutrient limitation outside the plume. Highest values of primary production occurred at stations where surface nutrient concentrations exhibited large deviations from conservative mixing relationships, indicating that depletion of nutrients was related to phytoplankton uptake. Mixing and advection were important in determining the location and magnitude of primary production maxima and nutrient depletion. In addition to growth within plume surface waters, enhanced growth and/or retention of biomass may have occurred in longer residence time waters at the plume edge and/or beneath the surface plume. Vertical structure of some plume stations revealed the presence of subsurface biomass maxima in intermediate salinity water that was depleted in nutrients presumably by uptake processes. Exchange between subsurface water and the surface plume apparently contributed to the reduction in nutrients at intermediate salinities in the surface layer. DIN (=nitrate+nitrite+ammonium) : PO₄ (=phosphate) ratios in river water varied seasonally, with high values in winter and spring and low values in late summer and fall. Periods of high DIN : PO₄ ratios in river nutrients coincided with cruises when surface nutrient concentrations and their ratios indicated a high probability for P limitation. N limitation was more likely to occur at high salinities and during late summer and fall. Evidence for Si limitation was also found, particularly in spring.     

Formation waters discharge to rivers near oil sands projects

Groundwater discharges in the western Canadian oil sands region impact river water quality. Mapping groundwater discharges to rivers in the oil sands region is important to target water quality monitoring efforts and to ensure injected wastewater and steam remain sequestered rather than eventually resurfacing. Saline springs composed of Pleistocene‐aged glacial meltwater exist in the region, but their spatial distribution has not been mapped comprehensively. Here we show that formation waters discharge into 3 major rivers as they flow through the Athabasca Oil Sands Region adjacent to many active oil sands projects. These discharges increase river chloride concentrations from river headwaters to downstream reaches by factors of ~23 in the Christina River, ~4 in the Clearwater River, and ~5 in the Athabasca River. Our survey provides further evidence for the substantial impact of formation water discharges on river water quality, even though they comprise less than ~2% of total streamflow. Geochemical evidence supporting formation water discharges as the leading control on river salinity include increases in river chloride concentrations, Na/(Na + Ca) ratios, Cl/(Cl + SO₄) ratios and decreases in ⁸⁷Sr/⁸⁶Sr ratios; each mixing trend is consistent with saline groundwater discharges sourced from Cretaceous or Devonian aquifers. These regional subsurface‐to‐surface connections signify that injected wastewater or steam may potentially resurface in the future, emphasizing the critical importance of mapping groundwater flow paths to understand present‐day streamflow quality and to predict the potential for injected fluids to resurface.     

Quantifying the sources of dissolved inorganic carbon within the sulfate-methane transition zone in nearshore sediments of Qi’ao Island,Pearl River Estuary,Southern China

The significance of the various biogeochemical pathways that drive carbon cycling and the relative fractions of dissolved inorganic carbon(DIC) produced by these reactions within the sulfate-methane transition zone(SMTZ) are still being debated. Unraveling these processes is important to our understanding of the benthic DIC sources and their contributions to the global carbon cycle. Here, we measure pore water geochemistry(chlorine, sulfate, methane, Ca~(2+), Mg~(2+), DIC and δ~(13)C-DIC) as well as solid geochemistry(sedimentary organic carbon(SOC) and δ~(13)C of SOC) in nearshore sediments from Qi'ao Island in the Pearl River Estuary of the Southern China Sea. Our analysis indicates that SOC originates from the mixing of carbon from terrestrial and marine sources, and that terrestrial materials dominate the net loss of SOC during the degradation of organic matter, especially at sites located near the river outlets. Sulfate reduction via SOC degradation is not appreciable in the upper sediment layer due to conservative mixing-dilution by freshwater. However, below this layer, the anaerobic oxidation of methane(AOM) and methanogenesis occur. Within the SMTZ, the δ~(13)C mass balance shows that the proportions of DIC derived from organoclastic SO_4~(2-) reduction(OSR) and AOM are 50.3% to 66.7% and 0.1% to 17.9%, respectively, whereas methanogenesis contributes 17.0% to 43.9%. This study reveals that the upward diffusion of DIC from ongoing methanogenesis significantly influences carbon cycling within the SMTZ in these estuarine sediments. As a result, we suggest that the plots of the ratio of change in sulfate to change in DIC in pore water should be used with caution when discriminating between sulfate reduction pathways in methane-rich sediments.