Structure and objectives of the Estonian Environmental Monitoring Program

The transition of Estonia from the fragmented character of environmental protection activities of the former Estonian SSR to a centralised national environmental monitoring program is underway. Estonian Environment Information Centre (EEIC) performed as a main developer of the Estonian Monitoring Program (EMP) structure, coordinates the operation of about 60 subprogrammes of EMP.     

An in vitro/in vivo screening assay as a sensitive tool to assess endocrine disruptive activity in surface water

Adult male fathead minnow were exposed for 14 or 28-days under flow-through conditions to undiluted filtered water samples from the rivers Meuse and Rhine in the Netherlands. The experiment included two vessels per treatment each containing 10 fish and samples of five fish were taken after 14 and 28 days. Additional groups were exposed to 17alpha-ethinylestradiol (EE2) as a reference and untreated drinking water as a negative control. Major endpoints examined included induction of vitellogenin (VTG) synthesis, VTG mRNA activity, hepato- and gonadosomatic indices (HSI and GSI) and gonadal histology. No significant difference was recorded in body weight or mean GSI values between the various treatments. Only exposure to Meuse water resulted in significantly higher HSI means after 14 days. Histological examination showed no apparent effects on gonadal tissue except for eosinophilic blood plasma in fish exposed to Meuse water or EE2. After 14 and 28 days, elevated VTG and VTG mRNA levels were measured in most livers of the fish exposed to Meuse water, but not in the fish exposed to Rhine water. This was confirmed by measuring estrogenic responses in the in vitro ER CALUX assay. Induction of VTG synthesis proved to be the most sensitive endpoint in the Non Spawning Male Fish Assay for in vivo detection of bio-available estrogenic activity supplementary to a sensitive in vitro assay. The other endpoints examined varied too much and required a higher number of fish or replicates to achieve sufficient power for statistical testing making them less animal friendly.     

Field reconnaissance and estimation of petroleum hydrocarbon and heavy metal contents of soils affected by the Ebocha-8 oil spillage in Niger Delta, Nigeria

Field reconnaissance of the Ebocha-8 oil spill-affected site at Obiobi/Obrikom in the Niger Delta region of Nigeria was carried out to assess the extent of damage to the terrestrial ecosystem and delimit the epicenter of oil spillage. Following three successive reconnaissance surveys, the area to be sampled was delimited (200 x 200 m2), and soil samples were collected using the grid method from three replicate quadrats at two depths, surface (0-15 cm) and subsurface (15-30 cm). A geographically similar area located 50 m adjacent to the oil-polluted area was used as a reference (control) site. Total hydrocarbon content (THC) and heavy metal concentrations were later determined in the laboratory by extraction and spetrophotemetric techniques. Generally, the THC of soils at surface and subsurface depths of the oil-polluted plots was 2.06 x 10(4) +/- 4.97 x 10(3) mg/kg and 1.67 x 10(3) +/- 3.61 x 10(2) mg/kg soil, respectively, (no overlap in standard errors at 95% confidence limit) while concentrations of heavy metals(Pb, Cd, V, Cu and Ni) were enhanced, especially at the surface. The high levels of THC and heavy metals may predispose the site, which hitherto served as arable agricultural land, to impaired fertility and possible conflagration. When concentrations of heavy metals reach the levels obtained in this study, they may become toxic to plants or possibly bio-accumulate, thus leading to toxic reactions along the food chain. While the spilled-oil may have contributed to the enhanced levels of the metals in the affected soils, physico-chemical properties of the soils, mobility of metals, and the intense rainfall and flooding that preceded the period of study may have also contributed in part to their enhanced concentrations. The presence of high hydrocarbon content may cause oxygen deprivation, which may result in the death of soil fauna by asphyxiation. There is, therefore, an urgent need to clear the affected site of these excess hydrocarbon deposits so as to enhance the rehabilitation process of the affected mat layer of soils. Other appropriate mitigating measures, such as subsequent monitoring of hydrocarbon levels at suitable intervals after the clean up activities, are also recommended, with reference to the findings of this study, for effective management of the affected area.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Metals, non-metals and PCB in electrical and electronic waste--actual levels in Switzerland

The chemical composition of waste of small electrical and electronic equipment (s-WEEE), a rapidly growing waste stream, was determined for selected metals (Cu, Sb, Hg etc.) and non-metals (Cl, Br, P) and PCBs. During a 3-day experiment, all output products and the s-WEEE input mass flows in a WEEE recycling plant were measured. Only output products were sampled and analyzed. Material balances were established, applying substance flow analysis (SFA). Transfer coefficients for the selected substances were also determined. The results demonstrate the capability of SFA to determine the composition of the highly heterogeneous WEEE for most substances with rather low uncertainty (2 sigma +/- 30%). The results confirm the growing importance of s-WEEE regarding secondary resource metals and potential toxic substances. Nowadays, the thirty times smaller s-WEEE turns over larger flows for many substances, compared to municipal solid waste. Transfer coefficient results serve to evaluate the separation efficiency of the recycling process and confirm--with the exception of PCB and Hg--the limitation of hand-sorting and mechanical processing to separate pollutants (Cd, Pb, etc.) out of reusable fractions. Regularly applied SFA would serve to assess the efficacy of legislative, organizational and technical measures on the WEEE.     

Column studies on transport of deicing additive benzotriazole in a sandy aquifer and a zerovalent iron barrier

Benzotriazole (BTA), a chemical with wide industrial applications, is a typical additive in deicer/anti-icer used at airport. To achieve a better understanding of the transport behaviour and environmental fate of BTA, laboratory column studies have been performed on subsoil samples from Oslo Airport, Gardermoen. To explore possibilities for aquifer remediation, BTA behaviour was also studied in a column of granular zerovalent iron (Fe(0)). The subsoil column study demonstrates a very limited retardation of BTA. Consecutive loadings of BTA of the subsoil column showed no change of the break-through curve (BTC) and complete desorption was observed. The sorption behaviour of BTA to metallic iron (Fe(0)) was rather complex. Considerable retardation was observed in the Fe(0) column and repeated BTA loading resulted in an earlier break-through. Between 20% and 50% of the input concentration was retained permanently in the iron (Fe(0)) column. The BTA sorption to metallic iron was found to be enhanced by chloride which lowered the break-through concentration (i.e the C/C(0) plateau). The fraction of BTA remaining in the iron column was found to vary with the flow rate, indicating a time dependant multilayer sorption mechanism. The steady increase in the amount of adsorbed BTA to the iron column during loading corresponds to a rather strong bonding of 4-15 BTA layers to the iron surface. A very slow desorption of BTA was observed; even after flushing with 753 pore volumes of BTA free water, 7.5% of the BTA remained in the column. A geochemical model was developed based on PHREEQC-2 to simulate the sorption and transport of BTA in the tested materials. The BTA sorption was modelled with Freundlich sorption isotherms, as earlier determined in batch experiments. A slight adjustment of the Freundlich parameters was required to fit the observed column break-through. However, our model was not able to simulate the long-term retainment of BTA in the granular iron columns. The simulations confirm the high mobility of BTA in groundwater aquifers and suggest that zerovalent iron could be used to retain a BTA plume, although oxidation of the sorbent might reduce the long-term performance of such a remediation scheme and slow desorption has been observed.     

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.     

Remediation of hydrocarbons in crude oil-contaminated soils using Fenton’s reagent

Sandy soil samples spiked with Bonny light crude oil were subsequently treated with Fenton's reagent at acidic, neutral, and basic pH ranges. Oil extracts from these samples including an untreated one were analyzed 1?week later with a gas chromatograph to provide evidence of hydrocarbon depletion by the oxidant. The reduction of three broad hydrocarbon groups-total petroleum hydrocarbon (TPH); benzene, toluene, ethylbenzene, and xylene (BTEX); and polycyclic aromatic hydrocarbon (PAH) were investigated at various pHs. Hydrocarbon removal was efficient, with treatment at the acidic pH giving the highest removal of about 96% for PAH, 99% for BTEX, and some TPH components experiencing complete disappearance. The four-ringed PAHs were depleted more than their three-ringed counterparts at the studied pH ranges.     

Hydrological Controls and Freshening in Meromictic Soap Lake,Washington, 1939-20021

Kallis, Jahn, Leo Bodensteiner, and Anthony Gabriel, 2010. Hydrological Controls and Freshening in Meromictic Soap Lake, Washington, 1939-2002. Journal of the American Water Resources Association (JAWRA) 46(4): 744-756. DOI: 10.1111/j.1752-1688.2010.00446.x Abstract: The chemically stratified layer of naturally formed meromictic lakes exhibits unusual and often extreme physical and chemical conditions that have resulted in the evolution of uniquely adapted species. The Columbia Basin Irrigation Project appears to have had a marked effect on the hydrology of Soap Lake, a meromictic lake in the Grand Coulee of central Washington. The relation of hydrology to salinity was assessed by analyzing water budgets before and after the introduction of the irrigation project. Before irrigation, water gains were balanced by losses; after irrigation began groundwater gains approximately doubled. To manage lake levels and reduce groundwater influx, wells were installed to intercept groundwater. Although the hydrological cycle has been restored to pre-irrigation conditions, the meromictic character of the lake continues to change. Interception wells remove 10 to 16 Mm³ of groundwater annually, but influx continues based on change in the monimolimnion. From 1958 to 2003 the chemocline descended 1.1 m and the volume of the monimolimnion from 698,000 m³ to 114,000 m³. Annual loss of volume is occurring at a rate of 1.9% since 1958. Although groundwater interception wells are maintaining the volume of the entire lake, the recession of the chemocline indicates that conditions that have maintained meromixis at Soap Lake are currently not in equilibrium.     

Dry FGD at United Power Association’s Stanton Station

The United Power Association’s dry FGD system at Stanton, North Dakota was the first utility-operated lime spray dryer to be put into service in the United States. At 60 MW in size, it utilizes a single spray dryer vessel with three rotary atomizers and a ten-compartment fabric filter. It is currently operating at better than expected efficiency and Is meeting state and federal air quality requirements. Start-up and operation have shown that certain areas of design and operating conditions are critical to reliable operation. Flue gas, slurry, and water distribution and mixing must be carefully controlled if reliable, long term operation is to be achieved. Likewise, water chemistry Is Important in the reagent preparation equipment. Start-up of the system was accomplished In a step-wise fashion to bring the baghouse on line first, followed by the spray dryer. The spray dryer was operated at gradually lower outlet temperatures until design conditions were met. Measures taken since start-up to ensure reliable operation, and operation over an eighteen month period are discussed. Both particulate and SO₂ emission performance are evaluated.