Untersuchung der Anwendungsmöglichkeiten von einigen komplexbildenden Ionenaustauschern zur Kupferabtrennung aus natürlichen Wässern und Abwässern

Application of Some Complexing Ion Exchangers for Copper Recovery from Natural Water and Wastewater The rational use of water resources is one of the urgent environmental control problems. These problems can be solved by the treatment of sewage. Removal of different non‐ferrous heavy metal ions from wastewater is of great importance. Besides, the selective complexing ion exchangers are of interest because of their good sorption properties. The present paper is devoted to the study of some complexing resins for copper recovery from natural water and sewage. The following carboxylic resins were studied: the cation exchangers KB‐2T, KB‐4 and the amphoteric ion exchangers ANKB 35, AMF‐2T, and AMF‐2S (manufacturer – “TOKEM” company, Kemerovo, Russia). The exchangers investigated differed from each other both by their functional groups and by their matrix physical structures. The copper recovery from CuCl₂‐, CuSO₄‐, and Cu(NO₃)₂‐solutions was studied in batch‐experiments (in presence of NaCl, Na₂SO₄, and NaNO₃). The initial copper concentration in the solutions was 0.0002...0.008 mol/L; pH values were 1.0...5.0. After equilibrium (24 h) the resins were separated from the solution. The copper concentration in the solutions after the sorption was determined by the photometrical method with pyridylazoresorcin (λ = 500 nm). On the basis of the experimental data distribution ratio, the separation factors, equilibrium constants, and stability constants of copper complexes in the exchanger phase were calculated. It was found out in this work that the amphoteric ion exchanger AMF‐2T of macroreticular structure is the most effective for the copper sorption from sewage.     

Bioremediation Management Reduces Mass Discharge at a Chlorinated DNAPL Site

Adaptive site management and aggressive bioremediation in the source zone of a complex chlorinated dense nonaqueous phase liquid (DNAPL) site reduced total chlorinated hydrocarbon mass discharge by nearly 80%. Successful anaerobic bioremediation of chlorinated hydrocarbons can be impaired by inadequate concentrations of electron donors, competing electron acceptors, specific inhibitors such as chloroform, and potentially by high contaminant concentrations associated with residual DNAPL. At the study site, the fractured bedrock aquifer was impacted by a mixture of chlorinated solvents and associated daughter products. Concentrations of 1,1,2,2‐tetrachloroethane (1,1,2,2‐TeCA), 1,1,2‐trichloroethane (1,1,2‐TCA), and 1,2‐dichloroethane (1,2‐DCA) were on the order of 100 to 1000 mg/L. Chloroform was present as a co‐contaminant and background sulfate concentrations were approximately 400 mg/L. Following propylene glycol injections, concentrations of organohalide‐respiring bacteria including Dehalococcoides and Dehalogenimonas spp. increased by two to three orders of magnitude across most of the source area. Statistical analysis indicated that reaching volatile fatty acid concentrations greater than 1000 mg/L and depleting sulfate to concentrations less than 50 mg/L were required to achieve a Dehalococcoides concentration greater than the 10⁴ cells/mL recommended for generally effective reductive dechlorination. In a limited area, chloroform concentrations greater than 5 mg/L inhibited growth of Dehalococcoides populations despite the availability of electron donor and otherwise appropriate geochemical conditions. After implementing a groundwater recirculation system targeting the inhibited area, chloroform concentrations decreased permitting significant increases in concentrations of Dehalococcoides and vinyl chloride reductase gene copies.     

Chloroethene Biotransformation in the Presence of Different Sulfate Concentrations

This paper aims to reconcile discrepancies among reports of dechlorination performance in the presence of sulfate, by analyzing data from the literature, presenting results from laboratory experiments performed with mixed anaerobic microbial cultures, and synthesizing respective findings. A complete set of metrics for dechlorination progress was developed and used in the analysis of selected field and laboratory studies. When differences in site and experimental conditions are accounted for and definitions of dechlorination completeness are harmonized, the inverse relationship between dechlorination performance and sulfate concentration becomes clearer. This relationship was investigated in detail with laboratory experiments on mixed anaerobic microbial cultures enriched with the same concentration of trichloroethylene (TCE) and different sulfate concentrations, equal to near zero (considered as the baseline culture), 30, 400, and 1100 mg/L. In all experiments, sulfate reduction proceeded concurrently with dechlorination. The observed behavior was bimodal, indicating a transition in dechlorination performance between 30 and 400 mg/L. Under low donor to acceptor stoichiometry conditions, TCE dechlorination was incomplete in all experiments after 14 days, while the percentage of TCE moles reduced to vinyl chloride was lower by about 50% in the experiments with high sulfate concentrations. When donor was added in excess to stoichiometry needs for TCE reduction, TCE dechlorination was complete in the baseline culture, while only little ethene was detected in the high sulfate concentration cultures. When all studies are considered together, it appears that the presence of sulfate does not preclude complete dechlorination but rather delays it. Data analysis also suggests that the proposed upper limit of 500 mg/L for the range of initial sulfate concentration that is not problematic for dechlorination should be revised to a lower value.     

Nährstoff- und Sauerstoffbilanz eines hochbelasteten Klärwerksableiters unter besonderer Berücksichtigung der submersen Makrophyten

Nutrient and Oxygen Balance of a Highly Polluted Treated Sewage Channel with Special Regard to the Submerged Macrophytes The changes of the concentrations of inorganic nitrogen compounds, orthophosphate, and oxygen were measured in the flowing wave along the flowing stretch of the Berlin treated sewage channel Wuhle monthly over a period of two years (1993/94) to estimate the nutrient and oxygen balances. This treated sewage channel is rich in nutrients and densely covered with submerged macrophytes. During the period of investigation in 1993 (1994), the effluent of the sewage treatment plant Falkenberg, which is lacking in adjustable nitrification and denitrification. contained in average 16.1 (12.7) mg/L of NH-N, 13.7 (9.4) mg/L of NO₃^?-N. 0.94 (0.69) mg/L of NO-N. and 0.36 (0.26) mg/L of PO-P. Due to the neglectable influence of other processes like nutrient uptake by submerged macrophytes and algae, desorption of ammonia or dilution, the changes of the concentrations of the inorganic nitrogen compounds are mainly influenced by nitrification and denitrification. The nitrification is mainly done by sessile nitrifiers in the treated sewage channel Wuhle. The nitrification rates. calculated from the decrease of the ammonium concentrations, were between 0.5 and 20 g/(m²d) related to the flowing stretch area. The ammonium concentrations decreased along the flowing stretch in average by 20 to 44%. The highest nitrification rates could be found at the stretches with a dense colonization with submerged macrophytes and a good oxygen supply due to low water depth and high flowing velocities. The denitrification rates, calculated from the decrease of the total of the concentrations of the inorganic nitrogen compounds, were between 0.5 and 23 g/(m²d) related to the flowing stretch area. The total loss of nitrogen due to denitrification was between 10 and 20% along the flowing stretch of the treated sewage channel Wuhle. This corresponds to a total amount of up to 530 kg nitrogen per day. The main part of the phosphorus occured as orthophosphate in concentrations between 0.04 and 0.87 mg/L of PO-P in the effluent of the treatment sewage plant Falkenberg. The orthophosphate concentration changed along the flowing stretch mostly in such a manner that it were at the same level at the end of the flowing stretch at the mouth into the river Spree. The self-purification capacity of the channel does not lead to a relevant reduction of the very high nutrient load under the present conditions. The rates of the photosynthetic production (P) and the community respiration (R) were calculated from the rates of the total changes of oxygen with regard to the physical aeration. The rates of the photosynthetic production were between 0 and 33 g/(m²d), the rates of the community respiration between 15 and 75 g/(m²d). Therewith, the Wuhle treatment sewage channel belongs to the very productive waters. A positive balance (P > R) could only be measured on two segments in May. The rates of oxygen production depend on the ratio width to depth of the water. It is possible that the positive influence of the submerged macrophytes on the oxygen balance also at higher biomasses than 250 g/m² (as dry weight) predominates at the segments with a favourable ratio. The portion of the oxygen input through diffusion along the flowing stretch and at the weirs was 30%, respectively, that of the photosynthic production 40% in summer. The rates of community respiration decreased along the flowing stretch by 50 to 90%. The nitrification had the main portion of the oxygen depletion in the Wuhle treated sewage channel with 60…80%. Despite the high biomass, the respiration of the submerged macrophytes had only a small portion of the total oxygen depletion. Nevertheless, the submerged macrophytes contributed to the nearly total oxygen depletion at the most densely covered segment 2 at night. The decrease of the content of particular organic material and the ammonia concentrations at the effluent of the sewage treatment plant, a diminishing of the biomass of submerged macrophytes by shading, and the widening of a few flowing stretches are demanded for the improvement of the oxygen balance of the Wuhle treated sewage channel.     

Biosorption of Cd(II), Ni(II) and Pb(II) from Aqueous Solution by Dried Biomass of Aspergillus niger: Application of Response Surface Methodology to the Optimization of Process Parameters

In this study, the biosorption of Cd(II), Ni(II) and Pb(II) on Aspergillus niger in a batch system was investigated, and optimal condition determined by means of central composite design (CCD) under response surface methodology (RSM). Biomass inactivated by heat and pretreated by alkali solution was used in the determination of optimal conditions. The effect of initial solution pH, biomass dose and initial ion concentration on the removal efficiency of metal ions by A. niger was optimized using a design of experiment (DOE) method. Experimental results indicated that the optimal conditions for biosorption were 5.22 g/L, 89.93 mg/L and 6.01 for biomass dose, initial ion concentration and solution pH, respectively. Enhancement of metal biosorption capacity of the dried biomass by pretreatment with sodium hydroxide was observed. Maximal removal efficiencies for Cd(II), Ni(III) and Pb(II) ions of 98, 80 and 99% were achieved, respectively. The biosorption capacity of A. niger biomass obtained for Cd(II), Ni(II) and Pb(II) ions was 2.2, 1.6 and 4.7 mg/g, respectively. According to these observations the fungal biomass of A. niger is a suitable biosorbent for the removal of heavy metals from aqueous solutions. Multiple response optimization was applied to the experimental data to discover the optimal conditions for a set of responses, simultaneously, by using a desirability function.     

Transformation of Trichloroethylene to Predominantly Non‐Regulated Products under Stimulated Sulfate Reducing Conditions

Anaerobic microcosms containing sediment and water were amended to generate a range of mass loadings of FeS. Microcosms were then spiked with trichloroethylene (TCE) and the concentration of TCE and possible volatile reaction products monitored over time. The lowest yields of TCE, as well as the lowest yields of reaction products regulated under the Safe Drinking Water Act (i.e., dichloroethylene isomers and vinyl chloride), were observed at FeS mass loadings at or above 20 g/L. Sixty eight days after spiking with TCE, selected microcosms were amended with sulfate and lactate, or sulfate, Fe(II), and lactate, and the effect of these amendments on TCE transformation and yield of regulated products was compared to microcosms that did not receive any amendments. Addition of sulfate, Fe(II), and lactate led to the greatest improvement on TCE depletion rates and the lowest yields of regulated reaction products compared with addition of sulfate and lactate, or no amendments. Analysis of kinetic modeling suggests that microbial and abiotic processes acted in concert to promote TCE transformation to a relatively low yield of regulated products in microbially active microcosms that contained high mass loadings of FeS.     

Enhancing Microbial Sulfate Reduction of Hydrocarbons in Groundwater Using Permeable Filled Borings

At a service station closed in 1993, groundwater contained benzene that persisted above the cleanup goal of 1 mg/L in zones depleted of background sulfate. The benzene and other petroleum hydrocarbons (PHCs) were present as much as 36 feet (11 m) below the water table and therefore remediation of a thick saturated zone interval was required. Microcosms using site sediments demonstrated that anaerobic benzene biodegradation occurred only if sulfate was added, suggesting sulfate addition as a remediation approach. Twenty-four boreholes (9.1″ diameter and 56′ deep) were drilled around four monitoring wells, in which benzene concentrations exceeded 1 mg/L. The boreholes were backfilled with a mixture of gravel and 15,000 pounds of gypsum (which releases sulfate as it dissolves) to create “Permeable Filled Borings” (PFBs). Concurrently, nine high pressure injections (HPIs) of gypsum slurry were conducted in other site locations (312 pounds of gypsum total). PFBs were expected to release sulfate for up to 20 years, whereas HPIs were expected to produce a short-lived plume of sulfate. Concentrations of benzene and sulfate in groundwater were monitored over a 3-year period in six monitoring wells. In two wells near PFBs, benzene concentrations dropped below the cleanup goal by two to three orders of magnitude; in one well, sulfate concentrations exceeded 500 mg/L for the most recent 18 months. Benzene concentrations in two other PFB monitoring wells declined by a factor of 2 to 4, but remained above 1 mg/L, presumably due to high-dissolved PHC concentrations and possibly greater residual PHC mass in adjacent sediments, and therefore greater sulfate demand. However, hydrogen and sulfur isotopic enrichment in benzene and sulfate, respectively, confirmed biodegradation of benzene and stimulation of sulfate-reducing conditions. Thus, it is hypothesized that the PHC mass in adjacent sediments will decline over time, as will dissolved PHC concentrations, and eventually benzene concentrations will decrease below the cleanup goal. Benzene in two HPI monitoring wells was below the cleanup goal for all but one sampling event before HPIs were conducted and remained below the cleanup goal after HPIs; there was no stimulation of sulfate-reducing conditions. It is concluded that sulfate released from PFBs contributed to declining benzene concentrations.     

Push‐Pull Tests for Estimating RDX and TNT Degradation Rates in Groundwater

In situ bioremediation is being considered to optimize an existing pump‐and‐treat remedy for treatment of explosives‐contaminated groundwater at the Umatilla Chemical Depot. Push‐pull tests were conducted using a phased approach to measure in situ hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and 2,4,6‐trinitrotoluene (TNT) degradation rates associated with various carbon substrates. Phase I included short‐duration transport tests conducted in each well to determine dilution rates and retardation factors for RDX and TNT. Phase II included aquifer “feedings” conducted by injecting 150 gallons of treated site groundwater amended with ethanol, corn syrup, lactose or emulsified oil (concentrations 10, 25 and 27 mM, respectively; 12% by volume for emulsified oil). Wells received up to 6 substrate “feedings” over the course of 3 months followed by monitoring dissolved oxygen, nitrate, Fe(II), and sulfate to gauge in situ redox conditions as indicators of anaerobic microbial activity. Phase III included push‐pull tests conducted by injecting 150 gallons of site groundwater amended with approximately 1000 µg/L RDX, 350 µg/L TNT, carbon substrate and a conservative tracer, followed by sampling over 8 d. Corn syrup resulted in the best RDX removal (82% on average) and the largest RDX degradation rate coefficient (1.4 ± 1.1 d^?1). Emulsified oil resulted in the best TNT removal (99%) and largest TNT degradation rate coefficient (5.7 × 10^?2 d^?1). These results will be used to simulate full‐scale in situ bioremediation scenarios at Umatilla and will support a go/no‐go decision to initiate full‐scale bioremediation remedy optimization.     

Zur Toxizität einfacher und komplexer Cyanide gegenüber Wasserorganismen

The toxic effects of alkali cyanide, complex cyanide-containing heavy metal salts—as of iron, cadmium, copper, nickel and mercury—were investigated according to standard methods with the aid of the test organisms Poecilia reticulata (guppy) as well as the green alga Ankistrodesmus falcatus (β- bis α-mesosaprobic). Since various complex compounds can be photolytically decomposed, also discontinuous light-dark phases were used. As discussed equilibrium calculations have shown, inter alia also the pH-value is important in the fish organisms used with different reactions to ions and molecularly dissolved compounds. The results are summarized in tables and graphic representations, the substances investigated being classified into groups with “strong” and “high” toxic actions.     

Pump‐and‐Treat Groundwater Remediation Using Chlorine/Ultraviolet Advanced Oxidation Processes

Comparative studies of the use of chlorine/ultraviolet (Cl₂/UV) and hydrogen peroxide/ultraviolet (H₂O₂/UV) Advanced oxidation processes (AOPs) to remove trichloroethylene (TCE) from groundwater in a pump‐and‐treat application were conducted for the first time at the full‐scale operational level at two water treatment facilities in Northern California. In these studies, aqueous chlorine replaced hydrogen peroxide in the AOP treatment step, where the oxidant is exposed to UV light to produce highly reactive radical species that degrade groundwater contaminants. TCE removal rates as a function of initial chlorine dose and pH were then determined. At the site where the natural pH of the water was 7.1, TCE was removed (to a concentration of less than 0.5 µg/L) for nearly every chlorine dose point tested, and pH adjustment slightly enhanced the treatment process at this facility. The second site had a high natural pH of 7.7, and here, TCE was not completely removed for any chlorine dose up to 5.7 mg/L, although TCE removal did increase when the chlorine dose increased between 0.9 and 3.6 mg/L. Residual TCE remaining in the water post‐Cl₂/UV was readily removed using active carbon filtration, which is part of the overall treatment train at this facility. These studies also verified that Cl₂/UV AOP did not interfere with the photolysis of N‐nitrosodimethylamine or result in an effluent acutely toxic toward Ceriodaphnia dubia. Comparative economic analysis revealed that the chemical costs associated with Cl₂/UV AOP were 25 to 50% of the costs associated with in place H₂O₂/UV AOP treatment.     

Scum in Nutrient Removal Plants: The Role of Carbon Sources in “Microthrix parvicella” Growth

Scum formation is a widespread problem in activated sludge nutrient removal plants. It often comes along with an excessive development of the filamentous bacterium “Microthrix parvicella” stabilizing the flotation process. As “M. parvicella” was found to depend on long‐chain fatty acids (LCFA) as sole carbon source not only in vitro but also in situ, some options of in‐situ substrate supply are discussed. Wastewater concentrations of fatty acids in the range of 2 to 15 mg L^‐1 and homologue concentrations from synthetic surfactant degradation below 10 mg L^‐1 rule out these substrates as source for excessive biomass production. They might, however, well be suitable for start‐up of a “M. parvicella” population. Build‐up of excessive biomass might rely on fatty acid supply originating in cell walls of lysed stationary phase bacteria of long residence time sludge fractions such as scum layers. Moreover, biogenic surfactants such as rhamnolipids have been proved to be an excellent carbon source for excessive biomass production in vitro.     

Removal of Phosphate in Aqueous Solution by Permethylated Poly(ethyleneimine) Entfernung von Phosphat mit permethyliertem Poly(ethylenimin) in wäßriger Lösung

The use of cationic, water-soluble, permethylated poly(ethyleneimine) (PMP) for the removal of phosphate ions was investigated using the Liquid-phase Polymer-based Retention (LPR) technique. The results showed that the retention values were dependent on the filtration factor (Z) and pH. In the presence of 10 mg/L phosphate and 1% PMP, 52% of the phosphate was retained at pH = 1.0 and 93% at pH = 8.5 for Z = 2. However only 11% of phosphate was retained at pH = 1.0 and 80% at pH = 8.5 for Z = 5. The maximum binding capacity of phosphate by 1% of PMP was 22 mg phosphate per gram of PMP at pH = 1.0 and 185 mg phosphate per gram of PMP at pH = 7.0. The influence of nitrate, chloride, and sulfate ions on the interaction of phosphate ions with PMP was also investigated. It was found that the interaction is strongly influenced by sulfate ions. In addition, viscosimetric measurements were performed and discussed.     

A Screening Procedure for Heavy Metals in Soil Extracts by Alcohol Dehydrogenase and Urease Inhibition Eine Screening-Methode für Schwermetalle in Extrakten aus Bodenproben,basierend auf der Inhibierung der Enzyme Alkoholdehydrogenase und Urease

A screening method for heavy metals in aqueous extracts of soil is presented which is based on inhibition of the enzymes urease and alcohol dehydrogenase. The method is suitable to detect cupric and mercury ions in concentrations below 0.01 mg/L and several other heavy metal ions in 1000 fold higher concentration. It is shown that the test may be used for screening of mercury ion concentrations exceeding 0.03 mg/L in aqueous solution when copper chelators are added to the test system. The usefulness of the presented tests to detect heavy metals eluted from soil was verified with samples from ore mining waste. The concentration of copper, lead, and zinc eluted from these samples to different amount was determined by atomic absorption spectrometry and was in good agreement with the enzyme inhibition data obtained with these samples.     

Der Einfluß der Komplexierung auf die Kupfertoxizität bei Blaualgen

Some aspects of the influence of copper speciation on toxicity for blue-green algae are reviewed. The experimental part concentrates on Oscillatoria redekei and Aphanizomenon gracile. The two investigated species produce strong extracellular copper complexing ligands: Oscillatoria redekei in the exponential and stationary growth phase, and Aphanizomenon gracile has a distinct detoxification capacity. The detoxification of copper by synthetic agents was investigated using ethylene-diamine-tetraacetic acid. Simultaneous addition of Cu²⁺ and Na₂EDTA gives evidence for a slow complexation reaction. Hence an excess of Na₂EDTA is necessary for a fast and complete detoxification of copper. Model calculations are reported to show that the precipitation of copper compounds is not probable under the conditions used.     

Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

In situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming groundwater contaminants into harmless by‐products. Owing to oxidant persistence, groundwater samples collected at hazardous waste sites may contain both the contaminant(s) and the oxidant in a “binary mixture.” Binary mixtures composed of sodium persulfate (2.5 g/L; 10.5 mM) and volatile organic compounds (VOCs) (benzene, toluene, m‐xylene, perchloroethylene, trichloroethylene) were analyzed to assess the impact on the quality of the sample. A significant decline (49 to 100%) in VOC concentrations was measured in binary mixtures using gas chromatography (GC) purge and trap, and GC mass spectroscopy headspace methods. Preservation of the binary mixture samples was achieved through the addition of ascorbic acid (99 to 100% VOC average recovery). High concentrations of ascorbic acid (42 to 420 mM) did not interfere in the measurement of the VOCs and did not negatively impact the analytical instruments. High concentrations of ascorbic acid favored the reaction between persulfate and ascorbic acid while limiting the reaction between persulfate and VOCs. If an oxidant is detected and the binary sample is not appropriately preserved, the quality of the sample is likely to be compromised.     

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.     

Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q_max) at pH 6 of 85.78 and 49.69 mg g^?1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO₃)₂, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH₂, and CH₃ in aliphatic structures, COO^? and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si? O groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.     

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.