Sirpa Herve

A survey of recent results in passive sampling of water and air by semipermeable membrane devices

Abstract A survey is presented of some recent results for passive sampling of water and air for trace organic contaminants using lipid-filled semipermeable membrane devices (SPMDs). Results of water sampling for trace organochlorine compounds using simultaneously exposed SPMDs and the most universally applied biomonitor (bivalves) are discussed. In general, the total amounts of accumulated analytes available for analysis in bivalves and SPMDs were comparable. However, SPMD controls typically had negligible levels of contamination, which was not always the case for transplanted bivalves, even after prolonged depuration prior to exposure. In surveys of the spatial trends of organochlorines at a series of sites, data from bivalves and SPMDs provided the same picture of contaminant distribution and severity. An exception was ionizable contaminants such as the chlorinated phenolic compounds and their transformation products found in pulp mill effluents. In these cases the two monitoring approaches compliment each other, i.e. what is not found in bivalves appears in SPMDs and vice versa. SPMDs have also been applied in environments where biomonitoring is not feasible. SPMDs have shown their utility in studies of trace levels of polyaromatic hydrocarbons by locating and characterizing point sources. An example is given of their application to the calculation of contaminant half-lives from aqueous SPMD residues, a direct measurement of the persistence of contaminants in an environmental compartment. Similarly, results of air sampling with SPMDs in a relatively pristine coastal location are cited which reveal a tremendous enhancement in p,p′-DDE relative to open ocean values.

Lipid-Filled semipermeable membrane devices and mussels as samplers of organochlorine compounds in lake water.

Semipermeable membrane sampling devices (SPMDs) and caged lake mussels (Anodonta piscinalis) were simultaneously deployed at four lake watercourse sites in Central Finland four weeks in August 1992. This study was part of the regular annual monitoring of the organochlorine compounds (OCC) in pulp-mill recipient watercourses of Finland with bivalves. Chlorohydrocarbons (CHCs), chlorophenol compounds (PCPs), chloroanisoles (PCAs) and chloroveratroles (PCVs) were analyzed from lipid extract of mussels and from the synthetic triolein lipid of the SPMDs. Hexane-diethyl ether (9:1, v/v) dialysis using polyethylene membrane was applied in dean up of the SPMD lipids and, for comparison, to six sets of the mussel fat. Dialysis recovered CHCs but not PCPs from the mussel fat. CHCs, PCPs, PCAs and PCVs were all recovered in dialysis of the SPMD lipid. Handling of SPMDs in the transport and deployment operations caused significant OCC contamination for the blank SPMDs. Similar trends were revealed in the OCC profiles for mussels ans SPMDs. An exception was the lack of PCPs appearing in SPMDs that did appear in mussels and in a complementary manner the appearance of the PCAs and PCVs in SPMDs.

Mussel incubation method for monitoring organochlorine pollutants in watercourses. Four-year application in Finland

Abstract Four week incubation of mussels followed with analyses has been developed to a sensitive method for monitoring chlorohydrocarbons, chlorophenols and aromatic chloroethers in watercourses. During four-year application at the Kymijoki river basin in Central and Southern Finland a decreasing trend of chlorophenol pollution, appearance of chlorocymenes, -cymenenes, other chlorohydrocarbons from pulp bleaching and bioaccumulation of chloroanisoles and -veratroles were shown. A continuing local PCB pollution was found and place of its origin traced. Use of combined samples in analysis to improve the economy of monitoring was applied successfully. Toxaphene components and toxic PCDD and PCDF congeners were absent in mussels incubated very near to the effluent pipe of activated sludge treatment plant of a kraft pulp mill.

Refractory organic pollutants and toxicity in pulp and paper mill wastewaters

This review describes medium and high molecular weight organic material found in wastewaters from pulp and paper industry. The aim is to review the versatile pollutants and the analysis methods for their determination. Among other pollutants, biocides, extractives, and lignin-derived compounds are major contributors to harmful effects, such as toxicity, of industrial wastewaters. Toxicity of wastewaters from pulp and paper mills is briefly evaluated including the methods for toxicity analyses. Traditionally, wastewater purification includes mechanical treatment followed by chemical and/or biological treatment processes. A variety of methods are available for the purification of industrial wastewaters, including aerobic and anaerobic processes. However, some fractions of organic material, such as lignin and its derivatives, are difficult to degrade. Therefore, novel chemical methods, including electrochemical and oxidation processes, have been developed for separate use or in combination with biological treatment processes.

Chloroaromatic pollutants in mussels incubated in two Finnish watercourses polluted by industry

Abstract Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo- p -dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between

Uptake of organochlorines from lake water by hexane filled dialysis membranes and by mussels

The distribution of organochlorines in aquatic ecosystem was followed by simultaneous incubation of mussels and solvent filled dialysis membranes. The uptake of organochlorines by the mussel represents both active and passive processes while the solvent filled membranes reflect the passive uptake. The active uptake by the mussel via food and the gills seems to be more important than the passive one since the mussel collected lipophilic organochlorine components more effectively than the solvent filled membranes.

Widespread occurrence and seasonal variation of pharmaceuticals in surface waters and municipal wastewater treatment plants in central Finland

The presence of five selected pharmaceuticals, consisting of four anti-inflammatory drugs, diclofenac, ibuprofen, ketoprofen, naproxen, and an antiepileptic drug carbamazepine, was determined at four municipal wastewater treatment plants (WWTPs) and in the receiving waterway in central Finland. The samples were taken from influents and effluents of the WWTPs and from surface water of six locations along the water way, including northern Lake Päijänne. In addition, seasonal variation in the area was determined by comparing the concentrations in the winter and summer. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations in the influents and effluents ranged from hundreds of nanogram per liter to microgram per liter while ranged from tens of nanogram per liter in northern parts of the waterway to hundreds of nanogram per liter in northern Lake Päijänne near the city area. In addition, the concentrations were higher in the winter compared to summer time in surface water due to decreased temperature and solar irradiation. On the other hand, higher concentrations of ibuprofen, ketoprofen, and naproxen were found in summer at the WWTPs, possibly due to seasonal variations in consumption. In conclusion, there are considerable amounts of pharmaceuticals not only in influents and effluents of the WWTPs but also in lake water along the waterway and in northern Lake Päijänne.

Study of organochlorine pollutants in snow at North Pole and comparison to the snow at North, Central and South Finland

Abstract Organic pollutants, especially polychlorinated hydrocarbons, phenols, guaiacols and catechols have been studied by analyses of snow samples from North Pole, May 1984. All of these pollutants were below the limit of determination which was estimated to be as fallout 0.1–0.05 μg/m 2 for individual compounds. For comparison, snow samples from Central Finland and South Finland 1983–1985 also showed non-detectable levels of chlorinated hydrocarbons but well measurable levels of chlorophenol compounds which were significantly higher at urban (heavy traffic) than rural and higher at South than Central Finnish places, respectively. One sample from Lapland, North Finland 1985, however, had no measurable amounts of chlorophenols like the North Pole sample.

Trends of organochlorine compounds in Finnish inland waters. Results of mussel incubation monitoring 1984-1998.

Caged common lake mussels (Anodonta piscinalis) have been used in the monitoring of organochlorine compounds in pulp and paper mill recipient watercourses of Finland annually from 1984 to 1998. Statistically significant decreasing trends of chlorophenols and chloroguaiacols originating from chlorobleaching were observed in all recipients in parallel with the decreasing discharges from the mills. Metabolites of chlorophenols, chloroanisoles and chloroveratroles had no or slightly increasing trends. Elevated PCB concentrations were measured in four watercourses. In two areas, PCBs were found to be significantly increasing, in two other cases they showed no trend. A mill producing recycled paper was apparently responsible for an increase of PCBs and DDE in recipient watercourses. Overall decreases were observed for other chlorohydrocarbons except for DDT. Material flows of chlorohydrocarbons were positively correlated with waterflows (Q) in some cases.

Uptake of chlorohydrocarbons from soil by lipid-containing semipermeable membrane devices (SPMDs)

Chlorohydrocarbons (CHCs) were surveyed in contaminated lake shore soil in Central Finland with polyethylene membranes containing synthetic triolein (SPMDs). High levels of hexachlorobenzene (HCBz) and PCBs were found in a significant number of the SPMDs exposed 28 days to 35 soil sampling locations along the 350 meter long shoreline. Distributions of HCBz and PCBs were different as demonstrated by two maximas of HCBz and four maximas of PCBs observed. Soil was also analyzed at selected locations for concentrations of CHCs, organic carbon (OC) and moisture. Steady state environmental fate modeling and simple equilibrium partition estimates based on analytical results both gave the same steady state concentrations in SPMD lipid for HCBz and PCB congeners. This indicates that HCBz and PCB concentrations in soil did not change significantly during the 28 day exposure. Uptake rates from soil to SPMD lipid were estimated and found not to correlate with moisture or OC. Approximation of the total contamination at the bulk shore soil gave 4.2 kg for HCBz and 3.4 kg for sum of PCBs.