Analysis of natural and synthetic estrogenic endocrine disruptors in environmental waters using online preconcentration coupled with LC-APPI-MS/MS.

This paper describes a fully automated online method for solid-phase extraction coupled with liquid chromatography and tandem mass spectrometry using atmospheric pressure ionization (LC-LC-APPI-MS/MS) to simultaneously detect selected dissolved natural and synthetic hormones at concentrations as low as 5 ng/L from aqueous matrices. The method shows excellent performance for the direct analysis of water and wastewater with respect to calibration curve linearity, analytic specificity, sensitivity, and carryover, as well as overall method accuracy and precision. With a runtime of 15 min, a minimum of 200 samples were analyzed using a single online solid-phase extraction (SPE) column without noticeable differences in system performance. Because of the ruggedness and simplicity of this system, generic methods can be easily developed and applied for the high-throughput analysis of a wide variety of compounds without the need to resort to laborious offline SPE sample preparation.

Butyltin species in benthic and pelagic organisms of the Saguenay Fjord (Canada) and Imposex occurrence in common whelk (Buccinum undatum).

The distribution and accumulation of butyltins in various tissues of 13 benthic and pelagic species living in the sub-Arctic Saguenay Fjord (Canada) were investigated. Butyltin contamination was ubiquitous in this ecosystem with tributyltin (TBT) biota to sediment accumulation factors (BSAF) ranging between 0.22 and 11, but without any important biomagnification between trophic levels. The large range of butyltin compounds accumulating within different tissues of the species collected from all trophic levels was from 7 to 1238 ng Sn g(-1) d.w. and indicates an exceptional contamination level only found in northern coastal areas exposed to an intensive traffic of commercial ships. Results show that bioaccumulation in organisms depends on three main factors: (1) the actual contamination level in their habitat, (2) their assimilation pathway by water, sediment or diet, and (3) their ability to metabolize TBT and excrete metabolites. By their lack of an efficient TBT degradation system, bivalves are subject to accumulate more butyltins (from 890 to 993 ng Sn g(-1) d.w. for TBT and from n.d to 138 ng Sn g(-1) d.w. for metabolites) whereas most burrow-dwelling organisms are able to degrade TBT and their butyltin levels ranged from 86 to 239 ng Sn g(-1) d.w. for TBT and from 7 to 106 ng Sn g(-1) d.w. for metabolites. Acadian redfish (Sebastes fasciatus) feeding preferentially on shrimps and small crustaceans rich in TBT showed a contamination level about three times higher than eelpout (Licodes vahlii). The latter species living in contact with the sediment and feeding on worms and other burrowing species had a lower proportion of TBT in their tissues. Finally, deleterious effects of butyltins in the Saguenay Fjord were assessed by the significant occurrence of Imposex in common whelk (Bucinum undatum) in two sites from Baie des Ha! Ha!. Results revealed that the effects of Imposex were accentuated close to the source of contamination, at Port-Alfred harbour, since the total of imposexed whelks collected at site A (the mouth of Baie des Ha! Ha!) was 12.5% and reached 52.6% at site B (Port Alfred). Although the incidence or frequency of imposex was low in site A compared to site B, the relative penile length index (RPL) values, a measure of the degree or severity of imposex, was similar at both sites indicating the presence of TBT with higher concentrations in site B.

Delayed gametogenesis and progesterone levels in soft-shell clams (Mya arenaria) in relation to in situ contamination to organotins and heavy metals in the St. Lawrence River (Canada).

There is a growing awareness that contaminants in the aquatic environment may alter steroid hormone levels and affect the reproductive success of the invertebrates. To verify if heavy metals and organotins affect sexual maturation in Mya arenaria, individuals were collected from July to November 1998, at different sites along the South coast of the St. Lawrence maritime estuary. Near the Rimouski harbour, clams showed high levels of tributyltin (TBT), DBT in the gonad, along with a lower gonado-somatic index [GSI=gonad wet weight (g)/body wet weight without shell (g)x100], low progesterone levels and a delay in sexual maturation when compared to the reference site. Sites that had intermediate levels of contaminants exhibited intermediate responses of hormones and sexual maturation stages. It is therefore suggested that TBT, DBT are endocrine disruptors in clams. Further studies will however be necessary to investigate in more details how contaminants as TBT can affect the steroid hormones production in the gonads of M. arenaria.

Sex alteration in soft-shell clams (Mya arenaria) in an intertidal zone of the Saint Lawrence river (Quebec, Canada).

The purpose of this study was to verify whether any changes in sex ratio might occur in soft-shell clams (Mya arenaria) located in an intertidal harbor zone located at the mouth of the Saguenay Fjord in the Saint Lawrence estuary (Baie Sainte-Catherine (BSC), Québec, Canada) likely to be contaminated by organotin compounds. Bivalves were harvested at the BSC harbor site and from two reference sites. Condition index (weight to length ratio), gonado-somatic index, sex ratio, vitellin-like proteins, organotin concentrations in gonad tissue, maturation stages of the gonads, the number of estradiol-17beta binding sites and the capacity of female gonad extracts to produce estradiol-17beta were determined in collected animals. Results showed that sex ratio in clams was significantly skewed toward males. Moreover, the condition and gonad-somatic indices, vitellin-like proteins in female gonads and the capacity of female gonads to produce estradiol-17beta were significantly reduced at the harbor site with respect to the reference sites. Maturation status of male gonads was clearly delayed at the harbor site. Additionally, gonad tissue contained tributyltin (TBT) at an average level of 109+/-18 ngSn/gdry wt. at the harbor site while organotins were not detected from the reference sites. Finally, female gonads had a higher number of unoccupied estradiol binding sites at the harbor site indicating low levels of this steroid in this tissue. Overall, this paper is first to report that clams collected in the vicinity of a TBT contaminated harbor are subject to masculinizing effects which seems to be consistent with biological effects that organotins are known to exert toward some other marine invertebrates.