Enhancement of PCBs biodegradation by sodium ligninsulfonate

Various mixtures of commercial PCBs (Aroclors) were rapidly biodegraded by Pseudomonas sp. 7509. The rate of biodegradation could be greatly enhanced by growing the cells in a stable PCB-ligninsulfonate emulsion. Microscopic examinations and growth studies suggested that biodegradation mainly took place at the PCB-water interface; the use of ligninsulfonate in the growth medium apparently allowed the cells to overcome the substrate limiting factor of surface area which, otherwise, might govern the subsequent rate of PCB degradation. Sodium ligninsulfonate was not degraded significantly in the PCB biodegradation process. Analyses of the culture broth, by gas chromatography, revealed that P. sp. 7509 could degrade 300 ppm of Aroclor 1254 after 18 days incubation. This degradation rate could be further enhanced by the addition of a small amount of Aroclor 1221 to the growth medium. A kinetic study, using resting cells, indicated that Aroclor 1221 was degraded much faster (980 μg h⁻¹ mg cell dry wt⁻¹) than the higher chlorinated Aroclor 1254 (43 μg h⁻¹ mg cell dry wt⁻¹). This finding was supported by manometric data which showed that regardless of the type of PCBs mixture used to grow the cells, the lower chlorinated PCBs were always oxidized faster than the higher chlorinated PCBs. The level of chlorination in a PCBs mixture therefore appears to be one of the major factors in determining its relative persistence to biodegradation.     

Organochlorine pesticide, polychlorinated biphenyl and heavy metal concentrations in wolves (Canis lupus L. 1758) from north-west Russia

The wolf Canis lupus is a major terrestrial predator in eastern Europe and, as a top carnivore, may be exposed to high concentrations of contaminants that are readily transferred through the food chain. Despite this, there are few published data on pollutant and pesticide levels in wolves. This study utilised tissues from animals legally killed by hunters for other reasons (animals were not killed for the purposes of this study) to carry out the only detailed investigation of contaminants in wolves in Europe and the first in animals from Eastern Europe. The livers of 58 wolves from the Tver and Smoliensk regions of northwest Russia (54°N 31°E to 57°N 35°E) were analysed for seven organochlorine pesticides, 24 PCB congeners, Aroclor 1254-matched summed PCBs (ΣPCBs), total mercury, cadmium and lead. Cadmium, most of the organochlorine pesticides and many PCB congeners were not detectable in any of the wolves. Hexachlorobenzene, alpha-HCH, pp′DDE, PCB congeners 118, 138, 149 and 156 and lead were detected in up to 6% of livers. Dieldrin, PCB congeners 153, 170 and 180, ΣPCBs and mercury were detected more frequently. Contaminant levels were generally low; maximum wet weight concentrations of any of the organochlorine pesticides, ΣPCBs and mercury were less than 0.1, 1 and 0.25 μg g⁻¹, respectively. PCB congeners 153, 170 and 180 accounted for 41% of the ΣPCBs. Dieldrin, ΣPCBs and mercury concentrations did not vary significantly between males and females nor between adult and juvenile (<12 months old) wolves apart from the ΣPCB concentration, which was on average five times higher in adults than juveniles. Liver residues were generally below the level normally associated with adverse effects except for lead levels which exceeded the critical 5 μg g⁻¹ dry wt. concentration in three of the 58 animals examined.     

Transport of C-labelled PCB compounds from sediment to water and from water to air in laboratory model systems

Tetra-, hexa- and octachlorobiphenyls were added to aquatic model systems composed of undisturbed sediment cores with an overlying water phase. Using impactor plates transport of the compounds from sediment to air was observed. About one per cent of the sediment-bound PCBs recovered in the systems left the water by jet drops from bursting bubbles. The transport of PCBs from the sediment to the air was nearly constant over time, with a transport rate of 0.62 μg · dm⁻² week⁻¹ for tetrachlorobiphenyl. Tetrachlorobiphenyl was mobile in systems with and without macroinvertebrates and in those fixed with HgCl₂. Hexa- and octachlorobiphenyls were transported from sediment to water mainly by bioturbation processes. The two latter substances had a higher adsorption to particles than tetrachlorobiphenyl. Compared to tetrachlorobiphenyl, more hexa- and octachlorobiphenyls accumulated in chironomids and tubificids.     

Determination of organochlorines in river sediment by capillary gas chromatography: Application to Dutch river sediment

An analytical method is described for the capillary gas chromatographic determination of 17 organochlorines, such as HCB, α-, β- and γ-HCH, aldrin, dieldrin, endrin, isodrin, telodrin, C-601 (1,2,3,4,7,7-hexachlorobicyclo-[2,2,1]-heptadieen-2,5), C-773 (1,2,3,4,5,7,7-heptachlorobicyclo-[2,2,1]-hepteen-2), heptachlor, β-heptachlorepoxide and the DDT-complex, in soil and river sediment. C-601 and C-773 are by-products of the aldrin and dieldrin synthesis. Several solvents were compared for the extraction from clay, peat and river sediment. Acetone gave the best results, also after a long period between spiking of soil and sediment samples with organochlorines and extraction. 14 Organochlorines were determined without interference from PCBs. The analysis of heptachlor, aldrin and p·p′-DDT can be interfered with by PCB components.The results of a monitoring program in tributaries of the Rhine River, Western Scheldt and in some harbour basins of Rotterdam are presented. HCB occurred frequently. The most contaminated sediment was found in a harbour basin near a pesticide producing plant. In this sediment the mean concentrations were 0.86 mg kg⁻¹ and 0.18 mg kg⁻¹ for dieldrin and endrin, respectively, on a dry weight basis.     

PCB dechlorination enhancement in Anacostia River sediment microcosms

In situ treatment of PCB contaminated sediments via microbial dechlorination is a promising alternative to dredging, which may be reserved for only the most contaminated areas. Reductive dechlorination of low levels of weathered PCB mixtures typical of urban environments may occur at slow rates. Here, we report that biostimulation and bioaugmentation enhanced dechlorination of low concentration (2.1 mg PCBs/kg dry weight) historical PCBs in microcosms prepared with Anacostia River, Washington, DC, sediment. Treatments included electron donors butyrate, lactate, propionate and acetate (1 mM each); alternate halogenated electron acceptors (haloprimers) tetrachlorobenzene (TeCB, 25 μM), pentachloronitrobenzene (PCNB, 25 μM), or 2,3,4,5,6-PCB (PCB116, 2.0 μM); and/or bioaugmentation with a culture containing Dehalococcoides ethenogenes strain 195 (3 × 10⁶ cells/mL). Dechlorination rates were enhanced in microcosms receiving bioaugmentation, PCNB and PCNB plus bioaugmentation, compared to other treatments. Microcosm subcultures generated after 415 days and spiked with PCB116 showed sustained capacity for dechlorination of PCB116 in PCNB, PCNB plus bioaugmentation, and TeCB treatments, relative to other treatments. Analysis of Chloroflexi 16S rRNA genes showed that TeCB and PCNB increased native Dehalococcoides spp. from the Pinellas subgroup; however this increase was correlated to enhanced dechlorination of low concentration weathered PCBs only in PCNB-amended microcosms. D. ethenogenes strain 195 was detected only in bioaugmented microcosms and decreased over 281 days. Bioaugmentation with D. ethenogenes strain 195 increased PCB dechlorination rates initially, but enhanced capacity for dechlorination of a model congener, PCB116, after 415 days occurred only in microcosms with enhanced native Dehalococcoides spp.     

Benthic oxygen demand in Lake Apopka, Florida

The benthic oxygen demand of Lake Apopka, Florida was determined using laboratory core uptake and flow through system techniques. The core-uptake for 5 stations in Lake Apopka averaged 67 mg O₂ m⁻²-h and partitioning experiments indicated that the oxygen uptake was primarily biological, with bacterial respiration dominating. No significant statistical correlations were found between core oxygen uptake rates and TKN levels (r = 0.33), percent volatile solids (r = 0.49), or macroinvertebrate densities (r = 0.59). Sediment oxygen uptake rates (D_B) were logarithmically related to flow rate in the following form D_B = − A + B In flow. Flow-through system sediment oxygen uptake at each station approached similar maximum uptake rates of 130 mg O₂ m⁻²-h at high (> 200 l h⁻¹) flow rates. Lake Apopka is an extremely shallow, wind mixed system and sediment uptake rates are expected to approximate this value during periods of intense wind mixing. The relatively low sediment uptake rates obtained for Lake Apopka, a hypereutrophic lake, supports the view that during eutrophication sediment respiration is progressively replaced by respiration in the water column.     

Use of large submerged chambers to measure sediment-water interactions

Submerged chambers were designed and constructed primarily to study in situ sediment phosphorus release in Shagawa Lake, Minnesota. Initial experiments indicated anoxic phosphorus release rates of 7 mg m⁻² day⁻¹. Oxygen consumption rates within the chambers were also measured; an average consumption rate of 0.17 g m⁻² day⁻¹ was obtained.     

The extent of reversibility of polychlorinated biphenyl adsorption

The extent of reversibility of PCB bonding to sediments has been characterized in studies on the partitioning behavior of a hexachlorobiphenyl isomer. Linear non-singular isotherms have been observed for the adsorption and desorption of 2.4.5.2′,4′,5′ hexachlorobiphenyl (HCBP) to 1100 ppm sediment suspensions. Partition coefficients, π(1 kg−1), for desorption from lake sediments (Saginaw Bay. Lake Huron. Michigan) are substantially greater (π_d 20.000–35.000) than those obtained for adsorption (π₄ 9000–14,000). HCBP was found to be more weakly adsorbed to montmorillonite (π_a − 3000, π_d 9000) and kaolinite (π_a 1000, π_d 3000) clay samples than to the natural sediment samples. Desorption results (π_d) for Saginaw Bay sediments were quite similar to π values (15,000–35.000) calculated from field measurements of aqueous and particulate PCB concentrations. For Saginaw Bay sediments and clay minerals partitioning appeared to be correlated both to sediment surface area and to sediment organic content. A regression analysis using both of these variables explained 90% of the observed variations. HCBP adsorption at 40 C (π_a 14,000) was significantly greater than at 1° C (π_a 6500) resulting in a calculated enthalpy of adsorption of +3.3 kcal mol⁻¹. Non-singular isotherm behavior was not found to be readily attributable to microbiological, kinetic or experimental effects. Evidence from consecutive desorption studies suggests that while HCBP adsorption may ultimately be reversible. release from sediments appeared to involve desorption along two distinct isotherms. These results have been interpreted in terms of possible similarities between the sorption properties observed in the distilled water systems of the present study and PCB bonding processes in natural water systems.     

Polychlorinated biphenyls (PCBs) in sediments of the southern Baltic Sea — trends and fate

Polychlorinated biphenyls (PCBs) have been determined in recent [0–1(2), 1(2)–5 and 5–10 cm deep layers] sediments from different sites of the southern Baltic Sea, including the Szczecin Lagoon, collected from May 1996 to October 1999, i.e. before and after the great flood in Poland of July/August 1997. The PCB distribution has been correlated with location and hydrological conditions as well as with organic carbon, algal pigments and their derivatives in the sediments. The sum of PCB (seven congeners) was equal to 1–149 ng/g dry wt., on average this was rather low (up to 40 ng/g). There was a decreasing trend in PCBs concentrations in the bottom sediments of the southern Baltic in 1996 but considerable amounts were still accumulated there. The flood of 1997 caused a distinct increase of PCB concentration level in the sediments, which again showed a decreasing trend in the next few years. This illustrates that at present the main source of PCBs for the southern Baltic are not a direct consequence of human activity, but from floods and heavy rains washing these compounds from land to the sea. Algae and algal detritus play an important role in the transport and distribution of PCBs in the southern Baltic. High correlation of PCBs with chlorophyll a derivatives — products of zooplankton grazing — indicates that PCBs are ingested by zooplankton with phytoplankton and then exuded with fecal pellets. PCBs bound to algal detritus or to fecal pellets in the water column are transferred to sediments, there they may be trapped either in a bonded and unchanged form or resuspended, remobilized and/or dechlorinated, depending on their properties and environmental conditions.     

Suppression of phosphorus release from lake sediments by the addition of nitrate

An assessment was made of the effectiveness of nitrate in reducing phosphorus release from the anoxic sediments of a small dimictic lake, White Lough, N. Ireland. Laboratory experiments on sediment cores showed that nitrate delayed and reduced phosphorus release with an input of 61 gN m⁻² causing complete suppression. The addition of 24 gN m⁻² of nitrate to the sediment of White Lough resulted in a delay and reduction of phosphorus release similar to that observed in the laboratory core experiments. Sediment release of iron in the lake was also delayed and reduced but manganese release and the rate of hypolimnetic deoxygenation were unaffected by the nitrate addition. Ammonium release rates in the sediment cores and in the whole lake experiment did not vary with nitrate input. Comparing the costs of using nitrate or iron/aluminium salts to suppress sediment phosphorus release indicated that the nitrate method was at least 80% more expensive.     

Hypolimnetic withdrawal in two north american lakes with anoxic phosphorus release from the sediment

Hypolimnetic withdrawal has been used to decrease eutrophication in two Connecticut lakes. This restoration technique is based on the forced discharge of nutrient-rich bottom waters in lakes with anoxic hypolimnia, while surface outflows are dammed. Internal phosphorus load amounted to 600 mg m⁻² summer⁻¹ before withdrawal. Most of this load probably originated from the sediment since the experimentally determined sediment phosphorus release rates of 2–12 mg m⁻² day⁻¹ can account for the internal load. The smaller lake responded to hypolimnetic withdrawal with decreasing epilimnetic and hypolimnetic phosphorus concentrations, decreased anoxia and internal loads. The larger lake also showed a tendency towards improvement which is, however, not statistically significant.     

The response of activated sludge to a polychlorinated biphenyl (KC-500)

A kind of polychlorinated biphenyl, Kanechlor 500, was selected as a representative industrial toxicant, and its effects on biochemical characteristics of the activated sludge and its behavior in the biological treatment process were observed at concentrations of 0, 1.5 and 10 μg l⁻¹.The presence of PCB in synthetic sewage resulted in changes in the microflora and aldolase activity of the activated sludge even at low concentration of PCB such as to be 1 μg l⁻¹, and it was also demonstrated that dosing PCB caused remarkable increase of the oxygen uptake activity. Furthermore, PCB was not found to undergo degradation to any appreciable extent during the aeration process nor as the result of anaerobic digestion, although low concentrations did not exert an influence on COD and BOD removal efficiency in the process. In synthetic sewage PCB was shown to undergo mobilization from the aqueous phase to the activated sludge as evidenced by a concentration factor on the order of 10³–10⁴.     

Sorption and accumulation of cadmium in the sediment of the Tama River

Cadmium contents in the water and the sediment samples collected from the Tama River and several branches were measured. Cadmium (above 0.005mgl⁻¹) was detected in only four of the water samples, while the sediment samples showed cadmium content of 1.0–9.8 μg g⁻¹ dry sediment. Cadmium concentration in the sediments of the main stream was correlated against ignition loss of the samples and it was found that 1 g of ignition loss (organic matter) corresponded to 35 μg of cadmium.The batch adsorption experiment in the laboratory using an aqueous solution of cadmium for 14 sediment samples with a higher concentration of cadmium indicated that the amount adsorbed by the sediment is highly dependent on the ignition loss. The amount adsorbed on unit mass of ignition loss q_IL could be correlated by a Freundlich-type equilibrium relation as where C is the equilibrium concentration in the aqueous phase ranging between 7 × 10⁻³ and 10 mg l⁻¹, while k_IL and n are equilibrium constants.The adsorption rate measurement showed that the intraparticle diffusion coefficient of cadmium in the sediment was about 1.1 × 10⁻⁶ cm²s⁻¹, which is of a reasonable order of magnitude assuming the pore diffusion mechanism inside the particle.The results suggest that suspended solid particles of high organic content in flowing water contribute significantly to the transport of cadmium along the river.     

Factors affecting the denitrification rate in two water-sediment systems

Effects of temperature, oxygen and nitrate concentrations of the overlying water, and the thickness of the sediment layer on the rate of denitrification in the sediment were investigated in two water-sediment systems, A and B. At 4°C, denitrification started after a prolonged lag period in contrast to nitrification which did not occur significantly. At 15°C, and particularly at 25°C, both processes proceeded readily. The disappearance of NO₂⁻ - N from the overlying water was more rapidly than that of NO₃⁻ - N.The denitrification rate was slightly reduced by increasing the dissolved oxygen concentration in the overlying water from 0 to approximately 2 mgl⁻¹. A further rise of the dissolved oxygen concentration had no further decreasing effect on the denitrification rate.The denitrification rate in sediment was dependent on the nitrate concentration in the overlying water approximating first order kinetics at lower concentrations, gradually becoming independent of the nitrate concentration at higher nitrate contents (zero order kinetics).When starting with a nitrate-nitrogen concentration of 25.2 mgl⁻¹, a sediment layer of 7 mm with A and 14 mm with B was roughly found to be involved in denitrification.Denitrification rates found in the present laboratory experiments were supposed to be considerably lower than those occurring under natural conditions as additional mechanisms for the transport of nitrate into sediments occurred in natural environments.     

Internal phosphorus loading in a shallow eutrophic lake

Internal loading of phosphorus has been implicated as a major eutrophicating factor in Long Lake, Washington (Kitsap County). As a result of such loading, summer total phosphorus concentrations approach or exceed 100 μgP l⁻¹. Most of the summer loading of phosphorus is thought to have been released directly from the rich, flocculent sediment in the mid and northern part of the lake as a result of high pH (up to 10) related to phytoplankton photosynthesis. The lake also supports a dense submersed macrophyte crop (areal weighted mean dry weight of about 220 g m⁻²) composed primarily of Elodea densa. Although excretion of phosphorus from healthy E. densa was found to be minimal, the potential contribution of P indirectly from sediment via macrophyte uptake and subsequent decomposition in the winter was on the order of 200–400 kg yr⁻¹ or about 25–50% of the external loading. Nevertheless, loading of phosphorus during predrawdown summers is thought to have originated largely as a direct release from sediment due to high pH. Estimates of sediment phosphorus release determined from laboratory experiments, mass balance and core analyses ranged from 2.2 to 5.6 mg m⁻² day⁻¹.As a component of the restoration program, the lake (mean depth of 2 m) was drawn down nearly 2 m for 4 months during the summer and fall of 1979. The lake's trophic status was expected to improve due to sediment consolidation and/or macrophyte reduction. The drawdown resulted in an 84% reduction in macrophyte biomass in 1980 but minimal sediment consolidation (0.1 m). Winter decomposition of the much smaller macrophyte crop, apparently provided insufficient phosphorus in the spring to stimulate phytoplankton and to enrich midlake sediments, which has probably occurred in previous years. Low water column pH during the postdrawndown summer of 1980 resulted from relatively low rates of plankton photosynthesis. During the summer of 1980 internal loading of phosphorus was reduced and total phosphorus remained below 50 μg l⁻¹.     

Gas production in aquatic sediments in the presence and absence of nitrate

In the overlying water of a water-sediment system the pH was controlled at 7.0, the nitrate-nitrogen concentration at 25.0 mg 1⁻¹ and the dissolved oxygen concentration above 6.1 mg t⁻¹. The temperature of the whole system was kept at 15°C. The average rate of nitrate removal from the system as a result of denitrification amounted to 160 mg NO₃⁻ -N m⁻² day⁻¹. By means of Eh measurements at various depths in the sediment, it was attempted to figure out the course of the penetration fronts of nitrate and oxygen in the sediment during 241 days of incubation. From these results the layer in which denitrification occurred was derived. The course of the denitrification zone was followed during the incubation period. As a result of the depletion of the available hydrogen donors in the sediment, oxygen reached the bottom of the sediment after 235 days of incubation.     

Distribution of particulate matter in relation to the thermal cycle in Lake Vechten (The Netherlands): The significance of transportation along the bottom

Throughout the thermal cycle of Lake Vechten (The Netherlands) the concentrations and chemical composition of particulate matter suspended in the water, deposited on the bottom near the shore and collected in sediment traps was measured. With regard to the distribution of particulate matter two significant periods during the thermal cycle could be distinguished. From May till mid-August a temperature gradient was present in the water column. During that period the average rate of increase in dry weight of bottom deposits and the sedimentation rate on that location were similar, i.e. lake wide 1.5 and 1.7 gm ²d⁻¹ respectively. This indicates a dominating role of settling particles in the building-up of the temporary shallow sediment, which resulted in the typical summer maximum of nearly 145 g m⁻². From mid-August onwards the concentration of this sediment zone decreased sharply coinciding with the disappearance of the temperature gradient. This removal was explained by the mechanism of enhanced turbulence, occurring when thermal homogeneity was reached, which initiated resuspension and subsequent transportation of the particles to greater depths. From light profiles it was inferred that the flux of particles was confined largely to the water layer of 1 m near the bottom. From comparison of the sedimentation rate in the central part of the lake with that in the shallow zone it could be estimated that compared to the particle flux in the open water towards profundal sediments, the flux along the bottom amounted during the thermal stratification period to an average of at least 42%.     

In situ sediment oxygen demand determinations in the Passaic River (NJ) during the late summer/early fall 1983

In situ sediment oxygen demand rate determinations were performed on the freshwater Passaic River system during the late summer/early fall of 1983. Values obtained ranged from non-detectable to 2.43 g m⁻² day⁻¹. The values obtained were compared with values obtained historically from similar locations. The dependency of the SOD rate on temperature was observed in consonance with the observations of other investigators performing laboratory experiments.     

Seasonality of diffusive exchange of polychlorinated biphenyls and hexachlorobenzene across the air-sea interface of Kaohsiung Harbor, Taiwan

Gaseous and dissolved concentrations of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) were measured in the ambient air and water of Kaohsiung Harbor lagoon, Taiwan, from December 2003 to January 2005. During the rainy season (April to September), gaseous PCB and HCB concentrations were low due to both scavenging by precipitation and dilution by prevailing southwesterly winds blown from the atmosphere of the South China Sea. In contrast, trace precipitation and prevailing northeasterly winds during the dry season (October to March) resulted in higher gaseous PCB and HCB concentrations. Instantaneous air-water exchange fluxes of PCB homologues and HCB were calculated from 22 pairs of air and water samples from Kaohsiung Harbor lagoon. All net fluxes of PCB homologues and HCB in this study are from water to air (net volatilization). The highest net volatile flux observed was + 172 ng m^− 2 day^− 1 (dichlorobiphenyls) in December, 2003 due to the high wind speed and high dissolved concentration. The PCB homologues and HCB fluxes were significantly governed by dissolved concentrations in Kaohsiung Harbor lagoon. For low molecular weight PCBs (LMW PCBs), their fluxes were also significantly correlated with wind speed. The net PCB and HCB fluxes suggest that the annual sums of 69 PCBs and HCB measured in this study were mainly volatile (57.4 × 10³ and 28.3 × 10³ ng m^− 2 yr^− 1, respectively) and estimated yearly, 1.5 kg and 0.76 kg of PCBs and HCB were emitted from the harbor lagoon surface waters to the ambient atmosphere. The average tPCB flux in this study was about one-tenth of tPCB fluxes seen in New York Harbor and in the Delaware River, which are reported to be greatly impacted by PCBs.     

Comparative bioaccumulation of mercury in two adjacent freshwater ecosystems

Mercury levels were determined in sediments, clams and representative fish species in two adjacent uncontaminated waterbodies situated on the Ontario Precambrian Shield. Food chain biomagnification of mercury occurred within both ecosystems. Significantly higher mercury levels were observed in most species resident in Tadenac Lake than in Tadenac Bay. For example, mean length adjusted fish mercury levels in Tadenac Lake and Tadenac Bay, respectively, were: smelt, 0.26 and 0.12 μg g⁻¹; rockbass, 0.34 and 0.18 μg g⁻¹; yellow perch, 0.29 and 0.12 μg g⁻¹; smallmouth bass, 0.55 and 0.25 μg g⁻¹ and northern pike 0.86 and 0.38 μg g⁻¹. The observed differences in fish mercury levels between the two sites cannot be explained in terms of differences in fish growth rates, lake trophic status or fish selenium levels, but appeared to be related to sediment mercury levels and ambient water quality.