Bio-reduction of arsenate using a hydrogen-based membrane biofilm reactor

Arsenate (As(V)) is a carcinogen and a significant problem in groundwater in many parts of the world. Since As(III) is generally more mobile and more toxic than As(V), the reduction of As(V) to As(III) is not a conventional treatment goal. However, reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation or complexation with sulfide or by adsorption to Fe(II)-based solids. A promising approach for reducing oxidized contaminants is the H2-based membrane biofilm reactor (MBfR). In the case of arsenate, the MBfR allows bio-reduction of As(V) to As(III) and sulfate to sulfide, thereby giving the potential for As removal, such as by precipitation of As2S3(s) or formation of Fe(II)-based solids. When As(V) was added to a denitrifying MBfR, As(V) was reduced immediately to As(III). Decreasing the influent sulfate loading increased As(V) reduction for a fixed H2 pressure. A series of short-term experiments elaborated on how As(V) loading, nitrate and sulfate loadings, and H2 pressure controlled As(V) reduction. Lower nitrate loading and increased As(V) loading increased the extent of As(V) reduction, but increased H2 pressure did not increase As(V) reduction. As(V) reduction was sensitive to sulfate loading, with a maximum As(V)-removal percentage and flux with no addition of sulfate. As(III) could be precipitated with sulfide or adsorbed to Fe(II) solids, which was verified by scanning electron microscopy and energy dispersive X-ray analysis.     

Methane production from the soluble fraction of distillers' dried grains with solubles in anaerobic sequencing batch reactors

Methane production from the soluble fraction of distillers' dried grains with solubles, a co-product of ethanol production, was studied in 2-L anaerobic sequencing batch reactors (ASBRs) under 10 different operating conditions. Methane production and chemical oxygen demand (COD) removal were quantified for a wide range of operating parameters. Chemical oxygen demand removals of 64 to 95% were achieved at organic loading rates ranging from 1.5 to 22.2 g COD/L x d, solids retention times from 8 to 40 days, and food-to-microorganism ratios ranging from 0.4 to 1.9 g COD/g volatile suspended solids (VSS) x d. Biogas methane content varied from 61 to 74%, with 0.29 L CH4 produced/g COD removed. Roughly 56% of the influent COD and 84% of the COD removed in the ASBRs was converted to methane. Microbial yield (Y) and decay (b) constants were determined to be Y = 0.126 g VSS/g COD removed and b = 0.032 day(-1), respectively. Methane produced from co-products can reduce the costs and fossil-fuel consumption of ethanol manufacture.     

Anaerobic bioconversion of carbon dioxide to biogas in an upflow anaerobic sludge blanket reactor

The increasing concentration of carbon dioxide (CO2)--the most dominant component of greenhouse gases--in the atmosphere has been of growing concern for many years. Many methods focus on CO2 capture and storage and there is always the risk of CO2 release to the environment. In this study, a new method to convert CO2 to biogas with a high content of methane (CH4) in an anaerobic system with a lab-scale upflow anaerobic sludge blanket reactor at 35 degrees C was developed. In a series of experiments, the reactor was run with and without CO2-saturated solutions including volatile fatty acids (VFAs) as sources of hydrogen. The concentration of dissolved CO2 in the influent solutions was 2.2-6.1 g/L, with corresponding chemical oxygen demand (COD) values of 2.6-8.4 g/L for the solutions. Overall CO2 removal values of 2.7-20 g/day (49-88% conversion) were obtained for the organic loading rates (OLR) and CO2 loading rates of 8-36 gCOD/L day and 6-26 gCO2/L x day, respectively with CH4 purity of above 70%. Also, VFA and COD removal were in the range of 79-95% and 75-90%, respectively. Methanogenic activities of the cultures with the concentrations measured as volatile suspended solids (VSSs) were 0.12-0.40 L CH4/gVSS x d with the highest value for the system containing acetic acid. This anaerobic method can be applied to reduce CO2 emitted to the atmosphere from a wide variety of industrial point sources with a value-added product, CH4.     

Simultaneous nitrification and denitrification of municipal wastewater in aerobic membrane bioreactors.

Simultaneous nitrification-denitrification (SND) of municipal wastewater was investigated in a laboratory-scale membrane bioreactor (MBR) operated at two different hydraulic retention times (HRTs), 0.5 and 1 day, dissolved oxygen 3.0 to 0.5 mg/L, and solids retention time (SRT) between 28 and 120 days. The organic loading rate (OLR) (0.11 to 0.64 kg chemical oxygen demand [COD]/m3/d) and influent soluble COD (SCOD)/ total Kjeldahl nitrogen (TKN) ratio (5 to 19) were varied by the addition of glucose. The ammonia-nitrogen and TKN removals were over 97%, and total nitrogen removal was approximately 89% in the MBR. The maximum specific nitrification rates (98 mg N/d/g VSS) and specific denitrification rates (81 mg N/d/g VSS) occurred at an SCOD/TKN ratio of 9.1. The optimum conditions for maximum total nitrogen removal by SND in a single reactor MBR have been found to be low dissolved oxygen (< 0.6 mg/L) and high OLR (approximately 0.64 kg COD/m3/d) at an HRT of 0.5 day and SRT of approximately 85 days.     

Assessment of the importance of sorption for steroid estrogens removal during activated sludge treatment

Distribution coefficients (K(d)) between water and activated sludge particles (f(oc)=27.7+/-0.1%) were measured for the steroid estrogens (SE), estrone (E1), 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in batch experiments. Experimental concentration levels ranged from environmentally realistic low ng/l to the high microg/l. In this range K(d)s were independent of their water concentration. The experimentally obtained K(d)s (with 95% confidence intervals) were 402+/-126 l/kg, 476+/-192 l/kg and 584+/-136 l/kg for E1, E2 and EE2, respectively. K(d)s were used to estimate the fraction of the total SE concentration that is expected to be sorbed in the activated sludge treatment tanks of a typical STP assuming equilibrium conditions. Assuming a suspended solids concentration of 4 g/l dissolved solids (ds), it was estimated that 61+/-9%, 66+/-13% and 70+/-6% of the total concentration of E1, E2 and EE2, respectively, would be sorbed during activated sludge treatment. The fraction of the SEs that was expected to be sorbed to suspended sludge particles in the effluents from a typical Danish STP was estimated to be only 0.20+/-0.06%, 0.24+/-0.10% and 0.29+/-0.07% of the total concentration of E1, E2 and EE2, respectively, at a suspended solids concentration of 5 mg/lds. For a typical STP the removal of steroid estrogens with excess sludge was estimated to be only 1.5-1.8% of the total loading if equilibrium conditions exists. Sorption is therefore not important for the fate of SEs in STPs compared to biodegradation.     

Reaction of arsenic vapor species with fly ash compounds: kinetics and speciation of the reaction with calcium silicates

In coal combustion systems, the partitioning of arsenic between the vapor and solid phases is determined by the interaction of arsenic vapors with fly ash compounds under post-combustion conditions. This partitioning is affected by gas–solid reactions between the calcium components of the ash particles and arsenic vapors. In this study, bench scale experiments were conducted with calcium compounds typical of coal-derived fly ash to determine product formation, the extent of reaction and reaction rates when contacted by arsenic oxide vapors. Experiments conducted with arsenic trioxide (As₄O_6(g)) vapors in contact with calcium oxide, di-calcium silicate and mono-calcium silicate over the temperature range 600–1000 °C indicated that these solids were capable of reacting with arsenic vapor species in both air and nitrogen. Calcium arsenate was the observed reaction product in all the samples analyzed. Maximum capture of arsenic occurred at 1000 °C with calcium oxide being the most effective of the three solids over the range of temperatures studied. Using a shrinking core model for a first order reaction and the results from intrinsic kinetic experiments conducted in air, the reaction rate constants were found to be 1.4×10⁻³exp(−2776/T) m/s for calcium oxide particles, 7.2×10⁻³exp(−3367/T) m/s for di-calcium silicate particles and 5.5×10⁻³exp(−3607/T) m/s for mono-calcium silicate particles. These results therefore suggest that any calcium present in fly ash can react with arsenic vapor and capture the metal in water-insoluble forms of the less hazardous As(V) oxidation state.     

Degradation of isobutanal at high loading rates in a compost biofilter

Biofiltration has been increasingly used for cleaning waste gases, mostly containing low concentrations of odorous compounds. To expand the application area of this technology, the biofiltration of higher pollutant loading rates has to be investigated. This article focuses on the biodegradation of isobutanal (IBAL) in a compost biofilter (BF) at mass loading rates between 211 and 4123 g/m3/day (30-590 ppm(v)). At mass loading rates up to 785 g/m3/day, near 100% removal efficiencies could be obtained. However, after increasing the loading rate to 1500-1900 g/m3/ day, the degradation efficiency decreased to 62-98%. In addition, a pH decrease and production of isobutanol (IBOL) and isobutyric acid (IBAC) were observed. This is the first report showing that an aldehyde can act as electron donor as well as acceptor in a BF. To study the effects of pH, compost moisture content, and electron acceptor availability on the biofiltration of IBAL, IBOL, and IBAC, additional batch and continuous experiments were performed. A pH of 5.2 reduced the IBAL degradation rate and inhibited the IBOL degradation, although adaptation of the microorganisms to low pH was observed in the BFs. IBAC was not degraded in the batch experiments. High moisture content (51%) initially had no effect on the IBOL production, although it negatively affected the IBAL elimination increasingly during a 21-day time-course experiment. In batch experiments, the reduction of IBAL to IBOL did not decrease when the amount of available electron acceptors (oxygen or nitrate) was increased. The IBAL removal efficiency at higher loading rates was limited by a combination of nutrient limitation, pH decrease, and dehydration, and the importance of each limiting factor depended on the influent concentration.     

Oxidative co-treatment using hydrogen peroxide with anaerobic digestion of excess municipal sludge.

The effect of an oxidative co-treatment on anaerobic digestion of a mixture of primary and waste activated sludge was investigated. The oxidant used in this study was hydrogen peroxide (H2O2). A maximum improvement in solid destruction of 15.2% was achieved in the overall process, with a dosage of 2.0 g H2O2/g influent volatile suspended solids (VSS(influent)). All configurations operated at this dosage also showed statistically significant increases in solids removal. A statistically significant enhancement in overall solids destruction was observed for the lower oxidant dosage (0.5 H2O2/g VSS(influent)). Surprisingly, for 1.0 g H2O2/g VSS(influent), only one of the three configurations involving oxidative co-treatment showed significant increases in solids destruction. Special attention was paid to the performance of this process relative to fecal coliforms destruction. Class A biosolids were obtained for all the different hydrogen peroxide dosages used when oxidative co-treatment is combined with a two-stage anaerobic digestion process.     

Volatilization of contaminants from suspended sediment in a water column during dredging

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.     

Microbial activity in a combined UASB-activated sludge reactor system

A combined upflow anaerobic sludge bed-activated sludge (UASB-AS) reactor system with consistently wasting of excess biomass was used to treat suspended-solids pre-settled piggery wastewater (COD=2000 mg l(-1), total Kjeldahl nitrogen TKN=400 mg l(-1), suspended solids=250-400 mg l(-1)). Thus, the activity of nitrogen-related microbial groups in each individual bioreactor was investigated. When the granules retention time (GRT) of 20-50 d in the UASB reactor, the solids retention time (SRT) of 10-25 d in the AS reactor and the recycle-to-influent ratio (Re) of 1 were maintained, the combined system removed 95-97% of chemical oxygen demand (COD), 100% of TKN and 54-55% of total nitrogen (TN). Denitrification and methanogenesis occurred in the UASB reactor so that both biochemical processes contributed to most of the COD removal and, complete nitrification (most of the TKN removal) occurred in the AS reactor. Compact granules with good settling abilities developed in the UASB reactor, and rapid rates of granulation of break-up granules in the UASB reactor were confirmed by experiments. The activity of nitrifiers and denitrifiers (an=0.68-0.87; adn=0.55-0.70) and the calculated specific nitrification and denitrification rates (qn=0.26-0.47 mg NH4+ -N mg VSS(-1)d(-1); qdn=0.046-0.076 mg NOx- -N mg VSS(-1)d(-1)) significantly increased with decreasing SRT and GRT, respectively. Accordingly, the combined UASB-AS reactor system should be regarded a promising alternative for the removal of organic carbon and nitrogen from piggery wastewater.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

污水深度处理微絮凝-D型滤池工艺运行性能与经济性分析

根据昆明市第一污水处理厂深度处理微絮凝-D型滤池工艺的运行数据,评价了工艺出水水质及总磷(TP)去除效果,同时分析了混凝剂投加量及药剂费用。结果表明,微絮凝-D型滤池工艺出水TP平均浓度为0.15 mg/L,最优水平值为0.05 mg/L,95%保证值为0.37 mg/L,TP平均去除率为63.6%。出水悬浮固体(SS)浓度95%保证值为10 mg/L。混凝剂聚合氯化铝(PAC)的投加量在1.5~4 mg Al2O3/L范围波动,去除单位TP的PAC投加量平均值为16.7 mg Al2O3/mg-P,投加比为2~8 mol-Al/mol-P。当投加比超过5时,出水TP浓度可达到0.3 mg/L以下。吨水PAC成本平均值为0.017元/t。     

TiO2光催化处理络合铜废水的实验研究

研究了以悬浮态TiO2为催化剂,在紫外光的作用下对络合铜废水进行光催化反应,分别考察了常温下TiO2投加量、反应时间、废水初始pH值、反应气氛等因素对处理效果的影响,并探讨了反应机理。结果表明：TiO2投加量为2 g/L,废水pH=4,300 W高压汞灯照射下,载入60 mL/min的空气反应40 min,120 mg/L EDTA络合铜废水的Cu（II）与COD的去除率达到最高,分别为96.56%和57.67%。     

TiO2光催化处理络合铜废水的实验研究

研究了以悬浮态TiO2为催化剂,在紫外光的作用下对络合铜废水进行光催化反应,分别考察了常温下TiO2投加量、反应时间、废水初始pH值、反应气氛等因素对处理效果的影响,并探讨了反应机理。结果表明:TiO2投加量为2 g/L,废水pH=4,300 W高压汞灯照射下,载入60 mL/min的空气反应40 min,120 mg/L EDTA络合铜废水的Cu(II)与COD的去除率达到最高,分别为96.56%和57.67%。     

Formation of Nitrate and Sulfate in the Plume of Berlin (8 pp)

Background, Aims and Scope Secondary inorganic aerosol (SIA), i.e. particulate sulphate (S(VI)), ammonium and nitrate (N(V)) is formed from gaseous precursors i.e., sulfur dioxide (S(IV)), ammonia and nitrogen oxides, in polluted air on the time-scale of hours to days. Besides particulate ammonium and nitrate, the respective gaseous species ammonia and nitric acid can be formed, too. SIA contributes significantly to elevated levels of respirable particulate matter in urban areas and in strongly anthropogenically influenced air in general. Methods The near-ground aerosol chemical composition was studied at two stationary sites in the vicinity of Berlin during a field campaign in summer 1998. By means of analysis of the wind field, two episodes were identified which allow to study changes within individual air masses during transport i.e., a Lagrangian type of experiment, with one station being upwind and the other downwind of the city. By reference to a passive tracer (Na+) and estimates on dry depositional losses, the influences of dispersion and mixing on concentration changes can be eliminated from the data analysis. Results and Discussion Chemical changes in N(-III), N(V) and S(VI) species were observed. SIA i.e., N(V) and S(VI), was formed from emissions in the city within a few hours. The significance of emissions in the city was furthermore confirmed by missing SIA formation in the case of transport around the city. For the two episodes, SIA formation rates could be derived, albeit not more precise than by an order of magnitude. N(V) formation rates were between 1.4 and 20 and between 1.9 and 59 % h-1 on the two days, respectively, and S(VI) formation rates were > 17 and > 10 % h-1. The area south of the city was identified as a source of ammonia. Conclusion The probability of occurrence of situations during which the downwind site (50 km downwind of Berlin) would be hit by an urban plume is > 7.4%. Furthermore, for the general case of rural areas in Germany it is estimated that for more than half of these there is a significant probability to be hit by an urban plume (> 8%). The S(VI) formation rates are higher than explainable by homogeneous gas-phase chemistry and suggest the involvement of heterogeneous reactions of aerosol particles. Recommendation and Outlook The possible contribution of heterogeneous processes to S(VI) formation should be addressed in laboratory studies. Measurements at more than two sites could improve the potential of Lagrangian field experiments for the quantification of atmospheric chemical transformations, if a second downwind site is chosen in such a way that, at least under particular stability conditions, measurements there are representative for the source area.     

Anaerobic digestion of raw and thermally hydrolyzed wastewater solids under various operational conditions

In this study, high-solids anaerobic digestion of thermally pretreated wastewater solids (THD) was compared with conventional mesophilic anaerobic digestion (MAD). Operational conditions, such as pretreatment temperature (150 to 170 degrees C), solids retention time (15 to 20 days), and digestion temperature (37 to 42 degrees C), were varied for the seven THD systems operated. Volatile solids reduction (VSR) by THD ranged from 56 to 62%, compared with approximately 50% for MAD. Higher VSR contributed to 24 to 59% increased biogas production (m3/kg VSR-d) from THD relative to MAD. The high-solids conditions of the THD feed resulted in high total ammonia-nitrogen (proportional to solids loading) and total alkalinity concentrations in excess of 14 g/L as calcium carbonate (CaCO3). Increased pH in THD reactors caused 5 to 8 times more un-ionized ammonia to be present than in MAD, and this likely led to inhibition of aceticlastic methanogens, resulting in accumulation of residual volatile fatty acids between 2 and 6 g/L as acetic acid. The THD produced biosolids cake that possessed low organic sulfur-based biosolids odor and dewatered to between 33 and 39% total solids. Dual conditioning with cationic polymer and ferric chloride was shown to be an effective strategy for mitigating dissolved organic nitrogen and UV-quenching compounds in the return stream following centrifugal dewatering of THD biosolids.     

Treatment of N,N-dimethylacetamide waste gas by a trickle-bed air biofilter.

The system performance of a trickle-bed air biofilter (TBAB) for treating N,N-dimethylacetamide (DMAC) waste gas was investigated under different gas flow rates and influent concentrations. In the pseudo-steady-state conditions, the DMAC elimination capacity increased but the removal efficiency decreased as the influent loading increased. More than 90% and 80% DMAC removal efficiencies are achieved for influent loadings below 20.2 and 34.5 g DMAC/m3/h, respectively. The TBAB appears to be an effective treatment process for controlling DMAC emission with low-to-medium loadings and the effectiveness could be maintained over a long-period operation.     

Performance and stability of two-stage anaerobic digestion.

The stability, capacity, and solids destruction efficiency of single versus two-stage anaerobic digestion was studied in bench-scale reactors using combined waste activated and primary sludge. Laboratory staged mesophilic digesters showed an improved volatile solids and volatile suspended solids destruction efficiency over a single-stage system (at the same total solids retention time [SRT]) of approximately 3.2 and 5.8 percentage points, respectively. To quantify stability and capacity, a new digester monitoring method was introduced that measured the digester maximum acetate utilization capacity, V(max,ac), and was used to investigate the potential for digester instability at different transient loadings. The ratio of the V(max,ac) value to the estimated acetate production rate for a given digester loading was termed the acetate capacity number (ACN). Values greater than 1.0 indicate excess acetate utilization capacity. The first stage of the laboratory two-stage mesophilic system (10-day SRT for each stage) had an ACN number of 1.3 compared with a value of 1.8 for the single-stage 20-day SRT digester. Thus, while a staged mesophilic system can improve solids destruction efficiency, it demonstrates a lower capacity for metabolizing highly variable loads.     

生物柴油促进原油污染砂粒释放油

对4种生物柴油促进原油污染砂粒释放油的效果进行了研究,并探讨了菜籽生物柴油投加量和砂粒粒径对促进效果的影响。结果表明,菜籽生物柴油的促进效果最好,8 h释放量达到73%,废油脂生物柴油的效果最差,仅为52%;生物柴油的促进效果随着投加量的增大而升高,当投加量超过海水体积的5%时促进效果不再明显增加;在生物柴油作用下,小粒径砂粒上原油的释放效果优于大粒径砂粒。     

Calibration of polyurethane foam (PUF) disk passive air samplers for quantitative measurement of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs): factors influencing sampling rates

PUF disk passive air samplers are increasingly employed for monitoring of POPs in ambient air. In order to utilize them as quantitative sampling devices, a calibration experiment was conducted. Time integrated indoor air concentrations of PCBs and PBDEs were obtained from a low volume air sampler operated over a 50 d period alongside the PUF disk samplers in the same office microenvironment. Passive sampling rates for the fully-sheltered sampler design employed in our research were determined for the 51 PCB and 7 PBDE congeners detected in all calibration samples. These values varied from 0.57 to 1.55 m3 d(-1) for individual PCBs and from 1.1 to 1.9 m3 d(-1) for PBDEs. These values are appreciably lower than those reported elsewhere for different PUF disk sampler designs (e.g. partially sheltered) employed under different conditions (e.g. in outdoor air), and derived using different calibration experiment configurations. This suggests that sampling rates derived for a specific sampler configuration deployed under specific environmental conditions, should not be extrapolated to different sampler configurations. Furthermore, our observation of variable congener-specific sampling rates (consistent with other studies), implies that more research is required in order to understand fully the factors that influence sampling rates. Analysis of wipe samples taken from the inside of the sampler housing, revealed evidence that the housing surface scavenges particle bound PBDEs.