Modelling of sequential groundwater treatment with zero valent iron and granular activated carbon

Multiple contaminant mixtures in groundwater may not efficiently be treated by a single technology if contaminants possess rather different properties with respect to sorptivity, solubility, and degradation potential. An obvious choice is to use sequenced units of the generally accepted treatment materials zero valent iron (ZVI) and granular activated carbon (GAC). However, as the results of this modelling study suggest, the required dimensions of both reactor units may strongly differ from those expected on the grounds of a contaminant-specific design. This is revealed by performing an analysis for a broad spectrum of design alternatives through numerical experiments for selected patterns of contaminant mixtures consisting of monochlorobenzene, tetrachloroethylene, trichloroethylene (TCE), cis-1,2-dichloroethylene (cis-DCE), and vinyl chloride (VC). It is shown that efficient treatment can be achieved only if competitive sorption effects in the GAC unit as well as the formation of intermediate products in the ZVI unit are carefully taken into account. Cost-optimal designs turned out to vary extremely depending on the prevailing conditions concerning contaminant concentrations, branching ratios, and unit costs of both reactor materials. Where VC is the critical contaminant, due to high initial concentration or extensive production as an intermediate, two options are cost-effective: an oversized ZVI unit with an oversized GAC unit or a pure GAC reactor.     

The use of a sequential leaching procedure for heavy metal fractionation in green liquor dregs from a causticizing process at a pulp mill

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).     

Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites

The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.     

Estimating catchment nutrient flow with the HBV-NP model: sensitivity to input data

The dynamic catchment model HBV-N has been further developed by adding routines for phosphorus transport and is now called the HBV-NP model. The model was shown to satisfactorily simulate nutrient dynamics in the R?nne? catchment (1,900 km2). Its sensitivity to input data was tested, and results demonstrated the increased sensitivity to the selection of input data on a subcatchment scale when compared with the catchment scale. Selection of soil and land use databases was found to be critical in some subcatchments but did not have a significant impact on a catchment scale. Although acceptable on a catchment scale, using templates and generalization, with regards to emissions from point sources and rural households, significantly decreased model performance in certain subcatchments when compared with using more detailed local information. A division into 64 subcatchments resulted in similar model performance at the catchment outlet when compared with a lumped approach. Adjusting the imported matrixes of the regional leaching of nitrogen, from agricultural land, against mean subcatchment water percolation did not have a significant impact on the model performance.     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

Enhanced experimental flexibility and control in ecotoxicological mesocosm experiments--a new outdoor and indoor pond and stream system

Scope The German Federal Environmental Agency has put into operation a new modular mesocosm system consisting of eight outdoor and eight indoor ponds and streams in order to investigate fate and effects of chemicals and municipal wastewater in aquatic ecosystems. General design and special characteristics are given to demonstrate the wide range of possibilities for experimental research. - General design. Each of the 16 streams with riffle and pool sections can be varied in length up to 106 m. The streams can be run as circular or flow-through systems at a flow velocity of 0.02 to 0.6 m/s. Physico-chemical standard parameters are measured on-line. The 16 ponds, which can be connected to the stream systems, are equipped with drainage and pore water-sampling devices for simulating processes in the littoral zone including influent and effluent ground water flow. Perspectives Since the highly flexible and controllable construction also allows treating a wide range of hydrological and ecological experiments external institutions are invited to submit proposals.     

Temporal trends of organochlorine contamination in Black Guillemots in Iceland from 1976 to 1996

The levels of several different persistent organochlorines (OCs) in Black Guillemots Cepphus grylle, collected during the summers of 1976-1996 at Breioafj?rour in W-Iceland, were investigated. The levels of about 40 different organochlorines (PCBs, DDTs, chlordanes, toxaphenes, HCH, HCB) were compared with respect to age, sex, fat content, and year of collection. The levels of PCBs correlated very closely with those of DDE, indicating long-range transport as the major source of these contaminants in Iceland, with the ratio PCBs/DDE mostly in the range of 2-5. Unlike the Gyrfalcon Falco rusticolus, the organochlorine levels did not seem to accumulate substantially with age, neither in males nor females. The variation in the levels of OCs at the age of 2 years was even greater than the variation in OC levels over an age range of 12 years. In immature birds the levels of PCBs, DDE, HCB and beta-HCH declined very slowly (T(1/2) from 12 to 20 years) over the years 1976-1996, whereas the levels of alpha-HCH and p,p'-DDT declined much faster. The levels of trans-nonachlor, alpha-chlordane, gamma-chlordane, oxychlordane, and toxaphene did not correlate with the year of collection. As the Black Guillemot is mostly a resident seabird, feeding mainly on small fish and invertebrates, this investigation should give a good indication of the temporal trends of organochlorine pollution at Breioafj?rour, Iceland, during this 20 year period and is likely to reflect baseline trends in the marine environment of the North-Atlantic Ocean.     

Anaerobic incorporation of the radiolabeled explosive TNT and metabolites into the organic soil matrix of contaminated soil after different treatment procedures

Four bioreactor designs were performed to evaluate the level of incorporation of 14C-labeled 2,4,6-trinitrotoluene (TNT) and metabolites into the organic soil matrix of different anaerobically treated contaminated soils. The contaminated soils were amended with molasses slivers (80:20% per weight) as auxiliary substrate to enhance microbial activity. After 5 weeks (bioreactors 1 and 2), 8 weeks (bioreactor 3) and 12 weeks (bioreactor 4) of anaerobic incubation, we determined 41%, 58%, 72%, and 54%, respectively, of the initially applied radioactivity immobilized in various soil fractions. After alkaline hydrolyses of the solvent-extracted soils, low quantities of radiolabel were found in the humic and fulvic acid fractions, whereas the bulk of 14C activity was found to be strongly bound to the humin fraction (solid soil residues). The amounts of solvent extractable radioactivity were 53%, 40%, 16%, and 29% for bioreactors 1, 2, 3, and 4, respectively. The level of TNT transformation at the end of the experiments was within 90-94%. Regarding the results presented in this study, we can assume that there is the possibility of high incorporation levels of TNT metabolites into the soil organic matrix mediated by microbial cometabolism under strictly anoxic conditions.     

Levels of dioxin-like compounds in sewage sludge determined with a bioassay based on EROD induction in chicken embryo liver cultures

A bioassay for the detection of dioxin-like compounds was used to estimate levels in sewage sludge from Swedish sewage treatment plants (STPs). The sludge extracts were HPLC-separated into three fractions containing a) monoaromatic/aliphatic, b) diaromatic (e.g. polychlorinated biphenyls [PCBs], polychlorinated dibenzodioxins and polychlorinated dibenzofurans [PCDDs/Fs]), and c) polyaromatic compounds (e.g. polycyclic aromatic hydrocarbons [PAHs]). The bioassay, which is based on EROD (7-ethoxyresorufin O-deethylase) induction in cultured chicken embryo livers detected dioxin-like activity in all unfractionated extracts and in the di- and polyaromatic fractions of all sludge extracts, but not in the monoaromatic/aliphatic fractions. The levels ranged between 6 and 109 pg bio-TEQ/g sludge (d.w.). In sediment samples from rural lakes in Sweden, levels of about 5 pg bio-TEQ/g (d.w.) have been found. The polyaromatic fractions of the sludge samples were potent in the bioassay, probably due to various PAHs and other polyaromatics in the sludge. The levels of six PAHs that are screened for in the sludge at Swedish STPs accounted for only 3-10% of the observed EROD-induction by the polyaromatic fractions. Consequently, many other polyaromatic EROD-inducing compounds were present in the sludge. Inclusion of a biological test like the chicken embryo liver bioassay in the screening of sludge would improve the ability to detect the presence of bioactive dioxin-like compounds. A theoretical estimation of bio-TEQ concentrations in farm-soil following long-term application of sludge with bio-TEQ concentrations similar to those observed in this investigation indicated that the bio-TEQ levels in soil would increase very slowly over time. The chicken embryo liver bioassay proved useful in assessing levels of dioxin-like compounds in sewage sludge and it gives valuable complementary information to chemical analysis data.