Recovery from acidification in European surface waters: a view to the future

There is now overwhelming documentation of large-scale chemical recovery from surface water acidification in Europe, but to date there has been little documentation of biological recovery. Modelling studies based on current emission reduction plans in Europe indicate that there will be further chemical recovery. The uncertainties in these scenarios mainly relate to the future behavior of nitrogen in the ecosystem and the effects of climate change. Four major climate-related confounding factors that may influence the chemical and biological recovery process are: i) increased frequency and severity of sea-salt episodes; ii) increased frequency and severity of drought; iii) increased turnover of organic carbon; iv) increased mineralization of nitrogen. International cooperative work to abate acidification has so far been very successful, but there is still a long way to go, and many potential setbacks. It is essential that future development of water chemistry and aquatic biota in acidified waterbodies continue to be monitored in relation to further emission reductions of S and N and future effects of climate change.     

Growth of Plants on TBT-contaminated Harbour Sludge and Effect on TBT Removal (10 pp)

Background Worldwide, large amounts of sediments have to be dredged annually from waterways and harbours. These sediments are sometimes polluted with a variety of toxic compounds. In some countries, including Belgium, the load with the biocide tributyltin (TBT) from ship coatings prohibits the dumping of harbour sludge into the sea. Land-based dumping is a commonly used alternative. Objective This research investigated the feasibility to use land-deposited harbour sludge for plant production. In a field trial, the growth of 38 more or less salt-tolerant plant species on low and high TBT-contaminated sediments was studied. The elimination of TBT from sludge with and without vegetation was compared. The uptake of TBT and its degradation products di- and monobutyltin (DBT and MBT) into harvest products under field conditions was determined. - Experimental Set-up. Sediments dredged in May 2003 from the brackish waters of the port of Antwerp were analysed in the laboratory for soil texture, pH, electroconductivity, sodium, magnesium, potassium, calcium, ammonium, nitrate, total nitrogen, chloride, sulphur and the organotins TBT, DBT and MBT. The sediments were lagooned for one year to dewater, desalinate and improve their structure. Salt-tolerant domestic and wild plants were selected and sown in May 2004. In August 2004, plants were harvested and the produced biomass was determined. Samples were taken from vegetated and non-vegetated top and bottom sediments and from plants growing above soil and analysed for TBT, DBT and MBT. Results The fresh sediments showed a good supply with nutrients and a neutral pH, but were rather saline (EC 14 mS cm-1 of the saturated paste extract). The salinity decreased to 3.7 mS cm-1 during lagoonation. The high and the low contaminated sediment had initially 43 and 1.6 mg TBT kg-1 dry weight, respectively. Besides TBT, several other contaminants were present in the sediments at critical levels. The biomass production of the plant species from the field trial ranged from 0.2 to 13 tons dry mass per hectare. Plants performing excellently were barley, sorghum, rape seed, a clover/grass mix and reed. If at all, a positive influence of TBT on plant growth was seen. TBT was degraded significantly faster (>40%) below barley. The uptake of TBT, DBT and MBT into stem and leaves of reed, grass and clover was very low, but measurable and not related to concentrations in soil. No uptake of TBT or its metabolites into corn of barley was found. Discussion This study confirmed former results: the toxicity of TBT to higher plants is low, and even high levels in soils would not be a hindrance for crop production. The removal of TBT seemed to be increased by both lagooning and plant growth, although the target values for sea dumping in use in certain European countries were not reached. A plausible explanation for the faster degradation of TBT under vegetation is that oxygen is a limiting factor, and plants dewater the soil, thus aerating it. The uptake of the organotins TBT, DBT and MBT into harvest products is probably due to attached soil particles. Conclusions To summarize, barley was the optimal species: it grew very well despite the salinity of the dredged sediments, it had a significantly positive effect on TBT removal; it showed no measurable uptake of TBT or the other butyltins into the harvested product; and it is a cash crop well established in European agriculture. Outlook The amounts of dredged sediments are high, and good soils are becoming increasingly rare. The feasibility of using dredged sediments for non-food production, such as energy crops, should be investigated by a critical risk assessment.     

Seasonal Fluctuation in Heavy Metal Pollution in Iran´s Siahroud River - A Preliminary Study (7 pp)

Background The management of its available water resources has become a key issue for Iran. During the last few decades, the water quality of Siahroud River in the coastal plain of the Caspian Sea in Gilan Province in Northern Iran has significantly degraded. The scarcity of water has been compounded by rapid population growth and increasing pollution from fertilizers, pesticides, and municipal and industrial wastes. One of the sources of this degradation is the movement of heavy metals from the river's watershed into the various water systems supported by the river, including the water system for Rasht City. Methods To study the magnitude of heavy metal pollution in the Siahroud River, seven heavy metals including Zn, Cu, Pb, Cd, Mn, Fe, and Ni were measured in duplicate from replicated water samples collected over five consecutive seasons and analyzed by Atomic Absorption Spectrometry. In situ measurements of pH were taken with the samples and total organic carbon (TOC) was analyzed by IR gas measurement. Results The results demonstrated that four of the seven heavy metals including Pb, Fe, Cd, and Mn exceeded permissible safe levels as established by the United States Environmental Protection Agency. Multivariate factor analysis suggested that industrial land-use was the main contributing factor for the high levels of Fe and Mn in the Siahroud River, whereas, Cd was principly from agricultural activities in the watershed. The data also suggested that pH and TOC had an important role in the behaviour of Pb and Mn, and that the elevated levels of these two heavy metals in Siahroud River was the consequence of other anthropogenic sources. Only negligible levels of Zn, Cu and Ni were detected. Finally, all the sampling stations were subjected to cluster analysis. The results indicated that three different zones could be distinguished according to the levels of pollution. In addition, it was shown that the urban areas did not have a significant impact on the heavy metal pollution in the river. This observation stems from the fact that the data from the sampling stations before and after Rasht City were not significantly different. Recommendation . Preventive measures need to be undertaken in the land-use systems and watersheds of the Siahroud River to reduce the pollution levels of Pb, Cd, Mn and Fe.     

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.     

Pilot-plant study of wastewater sludge decontamination using a ferrous sulfate bioleaching process.

The objective of this research was to investigate the performance of the ferrous sulfate bioleaching (FSBL) process in a pilot plant for decontamination and stabilization of wastewater sludge. Batch and continuous experiments, conducted with two 4-m3 bioreactors using indigenous iron-oxidizing bacteria (20% v/v of inoculum) with addition of 4.0 g ferrous sulfate heptahydrate per liter of sludge initially acidified to pH 4.0, were sufficient for effective heavy metal (cadmium, copper, manganese, zinc, and lead) removal yields. The average metal removal yields during the FSBL process were as follows: cadmium (69 to 75%), copper (68 to 70%), manganese (72 to 73%), zinc (65 to 66%), and lead (16%). The FSBL process was also found to be effective in removing both fecal and total coliforms (abatement > 5 to 6 log units). The nutrients content (nitrogen, phosphorus, and magnesium) were also preserved in decontaminated sludge.     

A theory on the mechanisms regulating the bioavailability of mercury in natural waters

A number of quantifiable properties of natural waters have been used by various scientists to 'explain' the Hg content in fish (e.g. pH, level of bioproduction, humosity, conductivity, calcium content, oxygen conditions, zinc and selenium content). This work presents a theory aimed at providing an explanation of the chemical mechanisms behind many established statistical relationships. The theory focuses on some equilibrium reactions and the causal relationships behind these reactions. The basic concept of the theory is that the activity of Hg(2+) in natural waters is essentially regulated by the activity of S(2-), which, in turn, is strongly affected by pH and redox conditions. Due to protonisation reactions, the S(2-) activity is very low at natural pH levels. The equilibrium between Hg(2+) and HgS(s) is given by the solubility constant Ks = 10(-52). This is an extremely low constant, which indicates that, in the presence of sulphide, essentially all Hg will appear as HgS(s). The Hg(2+) activity, and the Hg content in fish, can be increased if the S(2-) activity is decreased by lowering the pH and/or increasing the redox potential. Besides sulphide there are two other elements with a similar relationship towards Hg; namely, Se and Te (Ks = 10(-58) and Ks = 10(-70), respectively). The Hg(2+) concentration in natural waters varies quite widely, but is often about 5 ng litre(-1). This is a high concentration in these contexts. Such as high concentration can prevail only if the S(2-) (and/or the Se(2-)) activity is very small. In waters where the S(2-) and/or the Se(2-)) activity is high, e.g. from sulphide rocks in the drainage area, or if S(2-) and/or Se(2-) are added to the water, the Hg(2+) activity, and the Hg content in fish, will be effectively reduced.     

Clearance of PCDD/Fs via the gastrointestinal tract in occupationally exposed persons.

A digestive tract mass balance was performed on six men with high body burdens of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Intake via food was measured by analyzing duplicate portions of the food consumed by the volunteers and excretion via feces was determined by quantitative collection and analysis of the feces. Blood samples were taken to determine the current body burden. The results showed that the quantity of non-metabolized chemical excreted in the feces clearly exceeded the uptake via food for all of the 2,3,7,8-substituted PCDDs and some of the PCDFs, indicating a significant clearance across the gastrointestinal tract. The concentrations of these PCDD/F congeners in blood and feces were highly correlated (r > 0.8), demonstrating that the fecal PCDD/F content was determined by the body burden. The half lives in the test persons due to fecal clearance of non-metabolized chemical were estimated from the excretion rate and the current body burden and ranged between 10 years (Cl8DD) and 33 years (2,3,4,7,8-Cl5DF). These were compared with the overall contaminant half-lives due to all clearance processes which were calculated from the body burden and the decrease in blood concentrations measured over several years. The fecal clearance of non-metabolized PCDD/F contributed on average between 37% (2,3,7,8-Cl4DD) and 90% (Cl8DD) to the total elimination. This indicates that the gastrointestinal pathway plays a decisive role in the clearance of most 2,3,7,8-subsituted PCDD/F congeners.     

Absch?tzung der Quecksilberexposition

Zusammenfassung  Ein quecksilberkontaminierter Altstandort dient als Beispiel für eine umweltmedizinische Beurteilung der Belastung der im Umfeld wohnenden Personen durch Quecksilberimmissionen. Dabei wird die innere Exposition für sieben verschiedene Altersgruppen bezüglich der KontaktmedienBoden, Luft undNahrungsmittel anhand von konventionell festgelegten Szenarien abgesch?tzt und ein Vergleich mit den epidemiologischen Ergebnissen eines Humanmonitorings angestrebt. Die standortspezifisch und pfadspezifisch durchgeführte Expositionsabsch?tzung stützt sich auf cine Vielzahl von unterschiedlichen Probenehmern sowie auf über mehrere Jahre durchgeführte Konzentrationsmessungen in den aufnahmerelevanten Kompartimenten. Sowohl die Berechnungen als auch die epidemiologischen Untersuchungen zeigen eine leichte Erh?hung der Quecksilberexposition, gemessen an strengen Richtwerten.