Environmental fate of sulfonated-PCBs: Soil partitioning properties, bioaccumulation, persistence, and mobility.

Two new classes of PCB metabolites were recently discovered: sulfonated-polychlorinated biphenyls (sulfonated-PCBs) and hydroxy-sulfonated-polychlorinated biphenyls (OH-sulfonated-PCBs). These metabolites, originating from PCB degradation, seem to possess more polar characteristics than their parent compounds. However, no other information, such as their chemical identity (CAS number) or their ecotoxicity or toxicity, is available so far, although more than about one hundred different chemicals were observed in soil samples. In addition, their physico-chemical properties are still uncertain since only estimations are available. Here we show the first evidence on the fate of these new classes of contaminants in the environment, producing results from several experiments, to evaluate sulfonated-PCBs and OH-sulfonated-PCBs soil partition coefficients, degradation in soil after 18 months of rhizoremediation, uptake into plant roots and earthworms, as well as a preliminary analytical method to extract and concentrate these chemicals from water. The results give an overview of the expected environmental fate of these chemicals and open questions for further studies.

Synthesis of a new sulfonated-hexachlorobiphenyl standard for environmental analysis, ecotoxicological, and toxicological studies.

Sulfonated-polychlorinated biphenyls (sulfonated-PCBs) are a newly discovered class of PCB metabolites. They were observed for the first time in polar bear serum and lately, in soil, together with hydroxy-sulfonated-PCBs. Their presence is ubiquitous in soils, and their estimated physical chemical properties show high mobility in water, compared to the parent compounds. However, no single pure standards exist so far and therefore their quantification in the environmental matrices is not accurate. Additionally, pure standards are needed to experimentally determine their physical chemical properties, as well as the ecotoxicological and toxicological characteristics. In the present work, the challenging goal of preparing a polychlorinated biphenyl monosulfonic acid was achieved exploring different synthetic approaches, along which the selection of the starting material resulted in a crucial point. Using PCB-153 (2,2'-4,4'-5,5'-hexachloro-1,1'-biphenyl) the synthesis afforded, as the major species, a side compound. On the contrary, the use of PCB-155 (2,2'-4,4'-6,6'-hexachloro-1,1'-biphenyl), a symmetric hexachlorobiphenyl derivative showing chlorine atoms at all the ortho positions, gave the target sulfonated-PCB compound. In this case, sulfonation was successfully carried out through a two-step procedure, involving chlorosulfonylation and the subsequent hydrolysis of the chlorosulfonyl intermediate.

Bioaccumulation of PCBs and their hydroxy and sulfonated metabolites in earthworms: Comparing lab and field results.

Sulfonated and hydroxy-sulfonated PCBs were recently discovered by our group as new PCB soil contaminants, constituting about 1% of their parent compounds in soil. Here we investigate for the first time the bioaccumulation of these metabolites as well as hydroxy-PCBs and native PCBs in earthworms. A sequence of three experiments, at increasing complexity and ecological realism, were performed with four different earthworm species (Eisenia foetida Savigny, Lumbricus terrestris L, Allolobophora chlorotica Savigny and Aporrectodea caliginosa Savigny) exposed to contaminated soils. The first experiment confirmed that when exposing earthworms to soil contaminated with a single hexa-chlorinated congener (PCB 155), no formation of polar metabolites in earthworms could be detected. This allowed to plan the following two experiments, using a soil from a PCB contaminated site and rich in relatively high levels (10-130 µg kg-1) of hydroxy-, sulfonated-, and hydroxy-sulfonated-PCBs. Bioaccumulation factors (BAFs) and bioconcentration factors (BCFs) were then obtained in the second and third experiments, to compare the accumulation behavior of these chemicals in laboratory and natural conditions. Regressions between BAF/BCF and Log Kow/Log D, produced a variety of results, being generally significant between BCF and PCBs and not significant in the other cases. In general, the metabolites accumulated in earthworms with detectable concentrations in their tissues (8-115 µg kg-1), although sulfonated and hydroxy-sulfonated PCBs showed BAF and BCF values lower (up to two orders of magnitude) than those calculated for the parent PCBs, given their lower lipophilicity.