Levels of tin and organotin compounds in human urine samples from Iowa, United States.

Exposure to tin in the general US population is near ubiquitous, as determined using urinary tin levels measured by inductively coupled plasma mass spectrometry (ICP-MS). Urinary tin levels are associated with chronic health outcomes, such as diabetes; however, it is unclear if these associations are due to the presence of inorganic and organic forms of tin in urine. To address this knowledge gap, levels of total tin and several organotin compounds (OTCs) were measured in convenience urine samples from pregnant women and adults from Iowa, United States. Total tin and OTC levels in urine samples were quantified using ICP-MS and gas chromatography with pulsed flame photometric detection (GC-PFPD), respectively. ICP-MS detected tin in almost all urine samples from both study populations. Low levels of dibutyltin were detected in two out of fifty human urine samples. Importantly, storage of urine samples in plastic containers, but not HNO3-pretreated glass vials drastically reduced the recoveries of OTCs, in particular, tributyltin. Although their detection frequency is low, exposures to OTC should be considered when studying associations between human exposures to tin compounds and adverse health outcomes; however, urinary OTC levels measured in banked urine samples may not be suitable as biomarkers of OTC exposure.

Tributyltin-induced endoplasmic reticulum stress and its Ca(2+)-mediated mechanism.

Organotin compounds, especially tributyltin chloride (TBT), have been widely used in antifouling paints for marine vessels, but exhibit various toxicities in mammals. The endoplasmic reticulum (ER) is a multifunctional organelle that controls post-translational modification and intracellular Ca(2+) signaling. When the capacity of the quality control system of ER is exceeded under stress including ER Ca(2+) homeostasis disruption, ER functions are impaired and unfolded proteins are accumulated in ER lumen, which is called ER stress. Here, we examined whether TBT causes ER stress in human neuroblastoma SH-SY5Y cells. We found that 700nM TBT induced ER stress markers such as CHOP, GRP78, spliced XBP1 mRNA and phosphorylated eIF2α. TBT also decreased the cell viability both concentration- and time-dependently. Dibutyltin and monobutyltin did not induce ER stress markers. We hypothesized that TBT induces ER stress via Ca(2+) depletion, and to test this idea, we examined the effect of TBT on intracellular Ca(2+) concentration using fura-2 AM, a Ca(2+) fluorescent probe. TBT increased intracellular Ca(2+) concentration in a TBT-concentration-dependent manner, and Ca(2+) increase in 700nM TBT was mainly blocked by 50µM dantrolene, a ryanodine receptor antagonist (about 70% inhibition). Dantrolene also partially but significantly inhibited TBT-induced GRP78 expression and cell death. These results suggest that TBT increases intracellular Ca(2+) concentration by releasing Ca(2+) from ER, thereby causing ER stress.

Occurrence of tumors among gastropods Plicopurpura pansa (Gastropoda: Neogastropoda) in the Port of Manzanillo, Mexico.

In order to evaluate the health of Plicopurpura pansa, a species considered vulnerable, a population of this gastropod living in proximity to the port of greatest cargo movement in Mexico was monitored seasonally during 1 year. Morphometric characteristics and sexual proportion were recorded. A macroscopic analysis was carried out to detect malformations and imposex; a histological analysis was performed to evaluate disseminated and gonadal neoplasias; the presence/absence in soft tissues of butyltin species (BTs) as possible contamination agents was also estimated. A total of 508 P. pansa specimens were collected. The largest specimens were obtained in winter. The coefficients of determination inside the port were low (R2 = 0.453). In general, there was a greater proportion of females than males throughout the year. Distinctive foot malformations (tumors) were recorded, but without signs of imposex. The histological examination confirmed the presence of disseminated neoplasias in the foot and gonads of P. pansa in the Port of Manzanillo. The comparative analysis of the morphological and histological features of the studied gastropod population allowed us to recognize impact patterns in relation to proximity to the port. There were high concentrations of monobutyltin (MBT) and greater abundance of tumors in heavier specimens; this was associated with port proximity zones. P. pansa could therefore serve as a sensitive bioindicator of environmental health in marine systems.

TBT and its metabolites in sediments: Survey at a German coastal site and the central Baltic Sea.

Since the 1950s the organotin compound tributyltin (TBT) was intensively used in antifouling paints for marine vessels and it became of concern for the marine environment. Herein, we report on a study from 2015 on TBT and its metabolites monobutyltin (MBT) and dibutyltin (DBT) in sediments from the central Baltic Sea and a Baltic Sea coastal site with strong harbor activities (Warnemünde). Sublayers from a sediment core from the Arkona Basin were analyzed to investigate the long term organotin pressure for the Baltic Sea. For the central Baltic Sea total organotin (MBT+DBT+TBT) ranged from 100 to 500ng/g TOC with distinct areas of high organotin content probably due to historical inputs. For the coastal site total organotin ranged from 10,000 to 60,000ng/g TOC. MBT and DBT were the predominant organotin species detected. Overall, the data obtained indicate the progress of TBT degradation at the investigated sites.

Estrogen-mediated protection of the organotin-degrading strain Metarhizium robertsii against oxidative stress promoted by monobutyltin.

Dibutyltin (DBT) is a global pollutant characterized by pro-oxidative properties. The fungal strain Metarhizium robertsii can eliminate high levels of DBT efficiently. In this study, induction of oxidative stress as well as its alleviation through the application of natural estrogens during the elimination of DBT by M. robertsii were evaluated. During the first 24 h of incubation, the initial concentration of DBT (20 mg l-1) was reduced to 3.1 mg l-1, with simultaneous formation of a major byproduct - monobutyltin (MBT). In the presence of estrone (E1) or 17ß-estradiol (E2), the amounts of dibutyltin residues in the fungal cultures were found to be approximately 2-fold higher compared to cultures without estrogens, which was associated with the simultaneous utilization of the compounds by cytochrome P450 enzymes. On the other hand, MBT levels were approximately 2.5 times lower in the fungal cultures with the addition of one of the estrogens. MBT (not DBT) promotes the generation of O2-, H2O2, and NO at levels 65.89 ± 18.08, 4.04 ± 3.62, and 27.92 ± 1.95, respectively. Superoxide dismutase and catalase activities did not show any response of the M. robertsii strain against the overproduction of superoxide anion and hydrogen peroxide. Application of E1 as well as E2 ensured non-enzymatic defense against nitrosative and oxidative stress through scavenging of nitrogen and oxygen reactive species, and limited their levels from 1.5-fold to 21-fold, depending on the used estrogen.

Organotins' fate in lagoon sewage system: dealkylation and sludge sorption/desorption.

Organotin compounds (OTs) have been widely used for their biocidal properties and as stabilizers in various industrial applications. Due to their high toxicity, organotins are subject to many studies regarding their behavior in wastewater treatment plant and aquatic environment. However, few studies are available regarding their behavior in lagoon sewage system, although such treatment is commonly used for sewage treatment in low-population areas. The present study aimed at studying the fate of organotins (monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT)) in lagoon sewage system. Short-term experiments, carried out at lab scale, consisted in sampling sludge from aerobic stabilization ponds, and then quantifying sorption and desorption of the different organotin species, as well as their respective transformation, under defined operating conditions (e.g., tributyltin spike and dilution) simulating possible change in the surrounding environment of sludge in the lagoon. Results established that a very important percentage of the OTs was localized in the solid phase of the sludge (more than 98 %), whatever the operating conditions may be; however, transformation and locations of the three OT species differed according to the different conditions of sludge dilution, TBT spiking, and test duration. After dilution of lagoon sludge, TBT desorption from sludge was observed; it was supposed that dealkylation of TBT after desorption occurred rapidly and increased dissolved MBT and DBT in liquid phase; MBT sorbed subsequently on solid phase. The nature of the diluent (i.e., tap water or saline solution) appeared to slightly influence the sludge behavior. After TBT spiking, TBT was supposed to be rapidly sorbed but also transformed in DBT and MBT that would as well sorbed on the sludge, which explained the decrease of these species in the liquid phase. Tests aimed at studying long-term effect of TBT spiking demonstrated that the sorbed species could be remobilized and transformed after a dilution.

Baseline of the butyltin distribution in surface sediments (0-20 cm) of the Elbe estuary (Germany, 2011).

The concentrations of the butyltin (BT) species tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) were measured in the surface sediments (0-20 cm) at 29 sites of the Elbe estuary in 2011. TBT values ranged from 'undetectable' to 41 ng Sn g(-1) dry weight (d.w.) with the two highest values measured in the inner section of the estuary near the port of Hamburg (32 and 41 ng Sn g(-1) d.w.). TBT, DBT, and MBT showed significant decreases towards the estuarine mouth (Spearman's rho -0.660, -0.685, and -0.583, respectively, p<0.001). The degradation of TBT, assessed by the BT degradation index (BDI), showed a rising trend from the port of Hamburg towards the mouth of the estuary, though not a significant one (Spearman's correlation, p=0.066). Annual sedimentation rates did not show any significant correlations (Spearman's correlation) to BT pollution or to the butyltin degradation index (BDI).