Comparing total and accessible concentrations of hydrophobic organic contaminants in sediments and suspended particulate matter in the Danube River.

Contamination of aquatic ecosystems by hydrophobic organic contaminants (HOCs) is often assessed based on their concentrations in riverbed sediment and suspended particulate matter (SPM). However, total HOC concentration (CTOT) in sediment or SPM is of limited value for evaluating the exposure of benthic or pelagic organisms. The accessible HOC concentration (CAS) presents a useful parameter quantifying the overall pool of HOC in sediment or SPM available for fast partitioning to the water phase or biota. We applied a novel approach of ex situ sequential equilibrium partitioning with silicone elastomer sampler at a high sampler/SPM phase ratio to measure CAS of HOC in SPM from the Danube River. We compared CTOT and CAS in SPM and surface layer sediment collected at the same sites to evaluate whether HOC monitoring in the two matrices provides equivalent information on environmental quality. At most sites, there was a good agreement and correlation of organic carbon (OC)-normalised CTOT in SPM and sediment for polychlorinated biphenyls (PCBs) and the majority of organochlorine pesticides (OCPs). In contrast, CTOT of polycyclic aromatic hydrocarbons (PAHs) in SPM were up to a factor 10 lower in SPM than in sediment. Site-specific differences of OC-normalised CAS concentrations in SPM and sediments were observed for PCBs and OCPs, with accessibility mostly lower in SPM than in sediment. The highest accessibility in SPM was observed for PCBs, ranging between 15 and 30%. The accessibility of OCPs varied from 0 to 23%. SPM and riverbed sediment samples provide complementary but not mutually interchangeable information on HOC contamination.

Application of equilibrium passive sampling to profile pore water and accessible concentrations of hydrophobic organic contaminants in Danube sediments.

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:0) and accessible (CAS:0) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:0 concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:0 variability. CAS:0 in sediment ranged from 10 to 90% of the total concentration in sediment. CW:0 was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:0 values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

Investigation of cosolvent application to enhance POPs' mass transfer in partitioning passive sampling in sediment.

The freely dissolved concentration of persistent organic pollutants (POPs) is one of the most important parameters for risk assessment in aquatic environments, due to its proportionality to the chemical activity. Chemical activity difference represents the driving force for a spontaneous contaminant transport, such as water-aquatic biota or water-sediment. Freely dissolved concentrations in sediment pore water can be estimated from the concentrations in a partition-based passive sampler equilibrated in suspensions of contaminated sediment. Equilibration in the sediment/passive sampler system is slow, since concentrations of most POPs in the water phase, which is the main route for mass transfer, are very low. Adding methanol to sediment in suspension increases the POPs' solubility and, consequently, the permeability in the water phase. The resulting higher aqueous concentrations enhance POPs mass transfer up to three times for investigated POPs (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides) and shorten equilibrium attainment to less than 6 weeks. The addition of methanol to the aqueous phase up to a molar fraction of 0.2 changed the POPs equilibrium distribution ratio between sediment and passive sampler by less than a factor of two. As a result, the pore water concentrations of POPs, calculated from their amounts accumulated in a passive sampler, are affected by methanol addition not more than by the same factor.