Imposex incidence in gastropod species from the Colombian Caribbean Coast reveals continued and widespread tributyltin contamination after its global ban.

Organotin compounds (OTCs), such as tributyltin (TBT) and triphenyltin (TPhT), are released in aquatic environments from antifouling coatings and can cause imposex, an abnormal condition where female snails develop male sexual characteristics. This study investigates temporal variations in imposex incidence along the Colombian Caribbean coast following the 2008 global ban on TBT-based antifouling paints. Over a 12-year period, we assessed imposex in 1,384 adults snails from six species (58% female and 42% male) during 2012, 2016, and 2023. In 2012, just four years after the ban, imposex incidence in some sites reached 100% in the neogastropods Purpura patula, Stramonita haemastoma, Stramonita rustica, and Thais deltoideia. In 2016, imposex in some sites reached 81% for the mesogastropod Strombus pugilis and 39% for the neogastropod Melongena melongena. By 2023, imposex decreased for the first four neogastropods, persisted for S. pugilis, and increased for M. melongena only in Cartagena Bay and the Tolú marina. These findings indicate a general decline in imposex over time, aligning with the ban, but also suggest potential new sources of contamination as imposex rates increased in some previously unaffected areas.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) in human breast milk from Colombia: A probabilistic risk assessment approach.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) are ubiquitous environmental contaminants. They were produced in relatively large volumes in the last century and are now subject to long-term monitoring and regulated under the United Nations Stockholm Convention (SC) on persistent organic pollutants (POPs). Though restricted, human exposure is still a concern and in some regions of the globe the information on the health risk is limited. Sixty breast milk samples from nursing mothers were collected between 2014 and 2015, residing in Bogota, Cartagena, and Medellin, which are industrialized cities in Colombia. This is the first comprehensive study to determine the concentrations in breast milk of PBDEs (n = 7), PCBs (n = 29), and OCPs (n = 28) in Colombia. The detection frequency of POPs, including BDE-47, CB-138, CB-153, CB-156, and CB-180, as well as several OCPs such as chloroneb, aldrins, HCHs, DDTs, and heptachlor, was found to be 100% in all samples tested. The mean concentrations of the analyzed legacy POPs were ∑3DDTs (423 ng/g lw) > chloroneb (50.1 ng/g lw) > ∑2permetrins (17.5 ng/g lw) > ∑2aldrins (16.7 ng/g lw) > 29 PCBs (15.04 ng/g lw) > ∑2chlordanes (CHLs) (11.2 ng/g lw) ≈ ∑3endosulfans (11.1 ng/g lw) > ∑2heptachlors (2.43 ng/g lw) > 7PBDEs (2.1 ng/g lw) > ∑4HCHs (0.58 ng/g lw). The results of this study suggest that the concentrations of DDTs were present in breast milk samples from Colombia at levels comparable to those found in previous studies conducted in other countries such as Brazil, Uruguay, Chile, and various Asian countries. The concentrations of PBDE and PCB congeners, as well as many pesticides, were found to be significantly correlated with each other. This suggests that these substances may have similar sources of exposure. The strength of the pair correlation among concentrations of POPs was assessed using Spearman's correlation coefficients, which varied from r = 0.62 for the association between BDE-47 and CB-153, to a high correlation of 0.99 for the correlation between γ-Chlordane and heptachlor. This suggests that these POPs may share similar sources, such as diet. An exposure assessment model obtained by Monte Carlo simulation showed that infants were exposed to low concentrations of POPs with exception of p,p'-DDE and Aldrin, in which 25th, 50th and 95th percentiles were greater than the threshold reference values of non-carcinogenic effects suggested by US-EPA regulations while the 90th percentile of pg TEQ/Kg-bw/day for dl-PCBs was above of the tolerable daily intake (TDI) proposed by the World Health Organization (WHO). Therefore, the health risk of infants exposed to OCPs and dl-PCBs should be exanimated continually through biomonitoring programs in the Colombian population.

Adverse Health Effects and Mercury Exposure in a Colombian Artisanal and Small-Scale Gold Mining Community.

The aim of this study was, first of all, to associate the mercury (Hg) concentrations and respiratory functions of the gold miners in the artisanal small-scale gold mining (ASGM) environment in San Martín de Loba, Colombia. We carried out a cross-sectional study using a survey whereby we collected basic demographic information, occupational medical history, and applied two validated questionnaires (Q16 and SF36). We measured Hg levels in all volunteers using direct thermal decomposition-atomic absorption spectrometry. Univariate and bivariate statistical analyses were carried out for all variables, performing logistic regression to assess the effect of ASGM on health outcomes. Volunteers enrolled (n = 124) were between the ages of 20 and 84 years (84% miners and 79% males). No changes were found in the systolic blood pressure, diastolic blood pressure, and heart rate from the ASGM miners, in crude and adjusted statistical analyses. ASGM miners increased 8.91 (95% confidence interval, 1.55-95.70) times the risk of having these than of having neurotoxic effects. Concentrations of total whole blood mercury (T-Hg) in all participants ranged from 0.6 to 82.5 with a median of 6.0 µg/L. Miners had higher T-Hg concentrations than non-miners (p-value = 0.011). Normal and abnormal respiratory spirometry patterns showed significant differences with the physical role and physical function of quality-of-life scales (the (p-value was 0.012 and 0.004, respectively). The spirometry test was carried out in 87 male miners, with 25% of these miners reporting abnormalities. Out of these, 73% presented a restrictive spirometry pattern, and 27%, an obstructive spirometry pattern. The ASGM population had higher Hg concentrations and worse neurotoxic symptomatology than non-miners of the same community.

Biochemical and Hematological Markers in Workers with Chronical Exposure to Lead and Cadmium in Colombia.

The aim of the present study was to find if workers chronically exposed to lead (Pb) and cadmium (Cd) presented changes in their general health and in the clinical parameters of the population under study. We carried out a cross-sectional survey in a sample of informal workers in Cartagena, Colombia. The population under study was composed of male informal workers (≥18 years of age), with experience in their job, selected from occupational settings with potential exposure to Pb and Cd (i.e., mechanics, battery and garbage recyclers, and welders). The median age was 45 years (interquartile range (IQR), 33−53). The median blood Pb level (BLL) was 2 µg/dL (IQR, 0.76−6.22), and the median of blood Cd level (BCL) was 1.22 µg/L (IQR, 0.33−2.01). The study found that 33% of high exposure jobs with BLL > 5 µg/dL (n = 57), whereas in 'control' workers, this was 15.3% (n = 9). The highest BLLs were found in battery recyclers (82.1%; n = 23), followed by mechanics (37.3%, n = 22). In the logistic regression model adjusted by age, time on the job, smoking and elevated BCL and BLL increased 3.2 times (95% CI, 1.1−9.7) in mechanics and 29.6 times (95% CI, 7.2−145.6) in battery recyclers. This study found negative changes in the health of workers with higher chronic exposure to lead in Cartagena, Colombia.

Polycyclic aromatic hydrocarbons (PAHs) in human breast milk from Colombia: Spatial occurrence, sources and probabilistic risk assessment.

The diet is the main route that polycyclic aromatic hydrocarbons (PAHs) enter the body and measuring breast milk is one of the best ways to understand the maternal body burden and can be passed on to infants. In this study, it was determinate the concentrations of 23 PAHs in 60 milk samples taken from 3 cities in Colombia and to determine the potential routes of exposure and risk to human health. On average, concentration for the ∑PAHs across all locations was 186.6 ng g-1, lipid mass (LM), with city means of 260.1, 175.7, and 123.9 ng g-1 LM for Cartagena, Bogota and Medellin, respectively. Monte Carlo simulations were used to estimate the hazard quotient (HQ) and incremental lifetime cancer risk (ILCR) for infant dietary exposure to PAHs. HQs were below the safe thresholds (HQ = 1) while ILCRs were greater than the reference value equal to 10-6 (mg kg-1day-1). Dietary source assessment indicated that fish is a significant source of PAHs, with mothers that consumed fish at least once per week having ∼2.5 times greater PAH milk concentrations than other groups. While a disparity was also observed among consumers of exclusively marine (∑PAHs 198.5 ng g-1 LM) or freshwater fish (∑PAHs 85.7 ng g-1 LM). However, geographical considerations can be significant in this finding.

As3MT and GST Polymorphisms Influencing Arsenic Metabolism in Human Exposure to Drinking Groundwater.

The urinary arsenic metabolites may vary among individuals and the genetic factors have been reported to explain part of the variation. We assessed the influence of polymorphic variants of Arsenic-3-methyl-transferase and Glutathione-S-transferase on urinary arsenic metabolites. Twenty-two groundwater wells for human consumption from municipalities of Colombia were analyzed for assessed the exposure by lifetime average daily dose (LADD) (µg/kg bw/day). Surveys on 151 participants aged between 18 and 81 years old were applied to collect demographic information and other factors. In addition, genetic polymorphisms (GSTO2-rs156697, GSTP1-rs1695, As3MT-rs3740400, GSTT1 and GSTM1) were evaluated by real time and/or conventional PCR. Arsenic metabolites: AsIII, AsV, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) were measured using HPLC-HG-AFS. The influence of polymorphic variants, LADD and other factors were tested using multivariate analyses. The median of total arsenic concentration in groundwater was of 33.3 µg/L and the median of LADD for the high exposure dose was 0.33 µg/kg bw/day. Univariate analyses among arsenic metabolites and genetic polymorphisms showed MMA concentrations higher in heterozygous and/or homozygous genotypes of As3MT compared to the wild-type genotype. Besides, DMA concentrations were lower in heterozygous and/or homozygous genotypes of GSTP1 compared to the wild-type genotype. Both DMA and MMA concentrations were higher in GSTM1-null genotypes compared to the active genotype. Multivariate analyses showed statistically significant association among interactions gene-gene and gene-covariates to modify the MMA and DMA excretion. Interactions between polymorphic variants As3MT*GSTM1 and GSTO2*GSTP1 could be potential modifiers of urinary excretion of arsenic and covariates as age, LADD, and alcohol consumption contribute to largely vary the arsenic individual metabolic capacity in exposed people.

Arsenic exposure, profiles of urinary arsenic species, and polymorphism effects of glutathione-s-transferase and metallothioneins.

This study assessed the effects of polymorphic variants of gutathione-S-transferase and metallothioneins on profiles of urinary arsenic species. Drinking groundwater from Margarita and San Fernando, Colombia were analyzed and the lifetime average daily dose (LADD) of arsenic was determined. Specific surveys were applied to collect demographic information and other exposure factors. In addition, GSTT1-null, GSTM1-null, GSTP1-rs1695 and MT-2A-rs28366003 genetic polymorphisms were evaluated, either by direct PCR or PCR-RFLP. Urinary speciated arsenic concentrations were determined by HPLC-HG-AFS for species such as AsIII, AsV, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), and total urinary As (TuAs). Primary methylation index (PMI) and secondary methylation index (SMI) were also calculated as indicators of the metabolic capacity. Polymorphisms effects were tested using multivariate analysis, adjusted by potential confounders. The As concentrations in groundwater were on average 34.6 ± 24.7 µg/L greater than the WHO guideline for As (10 µg/L). There was a correlation between As concentrations in groundwater and TuAs (r = 0.59; p = 0.000). Urinary inorganic arsenic (%InAs) was associated with GSTP1, LADD, GSTP1*Age, GSTP1*alcohol consumption (r2 = 0.43; likelihood-ratio test, p = 0.000). PMI was associated with sex (r2 = 0.20; likelihood-ratio test, p = 0.007). GSTP1 (AG + GG) homozygotes/heterozygotes could increase urinary %InAs and decrease the PMI ratio in people exposed to low and high As from drinking groundwater. Therefore, the explanatory models showed the participation of some covariates that could influence the effects of the polymorphisms on these exposure biomarkers to As.

Linear and Nonlinear Calibration Methods for Predicting Mechanical Properties of Polypropylene Pellets Using Raman Spectroscopy.

A nondestructive and faster methodology to quantify mechanical properties of polypropylene (PP) pellets, obtained from an industrial plant, was developed with Raman spectroscopy. Raman spectra data were obtained from several types of samples such as homopolymer PP, random ethylene-propylene copolymer, and impact ethylene-propylene copolymer. Multivariate calibration models were developed by relating the changes in the Raman spectra to mechanical properties determined by ASTM tests (Young's traction modulus, tensile strength at yield, elongation at yield on traction, and flexural modulus at 1% secant). Several strategies were evaluated to build robust models including the use of preprocessing methods (baseline correction, vector normalization, de-trending, and standard normal variate), selecting the best subset of wavelengths to model property response and discarding irrelevant variables by applying genetic algorithm (GA). Linear multivariable models were investigated such as partial least square regression (PLS) and PLS with genetic algorithm (GA-PLS) while nonlinear models were implemented with artificial neural network (ANN) preceded by GA (GA-ANN). The best multivariate calibration models were obtained when a combination of genetic algorithms and artificial neural network were used on Raman spectral data with relative standard errors (%RSE) from 0.17 to 0.41 for training and 0.42 to 0.88% validation data sets.

Chemical and toxicological characterization of sediments along a Colombian shoreline impacted by coal export terminals.

Extraction, transport and utilization of coal spread out coal dust. Nowadays, Colombia is an important producer of this mineral in South America, being the Santa Marta area one of the largest coal exporting ports in the country. The aim of this work was to assess the pollutants levels and toxicity of shoreline sediments from this place. 16 PAHs and 46 elements were measured in nine locations during dry and rainy seasons. HepG2 cells were exposed to 1% sediment extracts and mRNA expression evaluated for selected genes. PAHs levels were greater during the rainy season. The highest ∑PAHs (89.9 ng g(-1)) appeared at a site located around 300 m far from the coast line at close proximity to the area where coal is loaded into cargo vessels for international shipments, being naphthalene the most abundant PAH. At Santa Marta Bay port, ∑PAHs were 62.8 ng g(-1) and 72.8 ng g(-1) for dry and rainy seasons, respectively, with greatest levels for fluoranthene. Based on sediment standards, most stations have poor condition regarding Cr, but moderate contamination on Cu, Pb and Zn. Sediments from the port and coal transport sites, the most polluted by PAHs and metals, induced CYP1A1 and NQO1 during the dry season. Data showed the sediments from this shoreline have bioactive chemicals that determine their toxicological profile.

Occurrence of perchlorate in indoor dust from the United States and eleven other countries: implications for human exposure.

Perchlorate is a widespread environmental contaminant and potent thyroid hormone disrupting compound. Despite this, very little is known with regard to the occurrence of this compound in indoor dust and the exposure of humans to perchlorate through dust ingestion. In this study, 366 indoor dust samples were collected from 12 countries, the USA, Colombia, Greece, Romania, Japan, Korea, Pakistan, Kuwait, Saudi Arabia, India, Vietnam, and China, during 2010-2014. Dust samples were extracted by 1% (v/v) methylamine in water. Analyte separation was achieved by an ion exchange (AS-21) column and analysis was performed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The overall concentrations of perchlorate in dust were in the range of 0.02-104µg/g (geometric mean: 0.41µg/g). The indoor dust samples from China contained the highest concentrations (geometric mean: 5.38µg/g). No remarkable differences in perchlorate concentrations in dust were found among various microenvironments (i.e., car, home, office, and laboratory). The estimated median daily intake (EDI) of perchlorate for toddlers through dust ingestion in the USA, Colombia, Greece, Romania, Japan, Korea, Pakistan, Kuwait, Saudi Arabia, India, Vietnam, and China was 1.89, 0.37, 1.71, 0.74, 4.90, 7.20, 0.60, 0.80, 1.55, 0.70, 2.15, and 21.3ng/kgbodyweight (bw)/day, respectively. Although high concentrations of perchlorate were measured in some dust samples, the contribution of dust to total perchlorate intake was <5% of the total perchlorate intake in humans. This is the first multinational survey on the occurrence of perchlorate in indoor dust.

Near-infrared chemical imaging slope as a new method to study tablet compaction and tablet relaxation.

Near-infrared chemical imaging (NIR-CI) spectra of lactose monohydrate tablets were acquired and the spectral slope from each pixel in the data hypercube was used to assess tablet compaction and relaxation. Tablets were prepared at compaction pressures of 100, 300, and 500 MPa using un-lubricated and magnesium stearate lubricated lactose monohydrate. Results show that NIR slope distribution is a function of applied compaction forces and magnesium stearate lubrication. The distribution of NIR slope values was studied using histograms and statistical parameters. The mean slope value yields a linear calibration curve that predicts tablet compaction pressure as a function of spectral slope. The NIR-CI slope measurements were also used to study tablet relaxation, which occurs as tablets release some of the stored energy from compression. The NIR-CI slope method provides a qualitative description of the relaxation process and provides quantitative information describing relaxation through time.

Polycyclic aromatic hydrocarbons and their hydroxylated metabolites in fish bile and sediments from coastal waters of Colombia.

Sediments and fish bile collected from the Atlantic coastal waters of Colombia were analyzed for 16 parent polycyclic aromatic hydrocarbons (PAHs), and 23 hydroxylated PAHs (OH-PAHs), respectively. Sediments contained overall mean SigmaPAH concentrations of 2090, 234 and 170 ng/g, dry wt, for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The mean concentration of the summed OH-PAHs in fish bile was 1250, 180 and 64.1 ng/g bile wt for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The results suggest that Cartagena Bay is heavily polluted by PAHs, and that exposure to high concentrations of PAHs together with other factors could contribute to the decreased health of fish living in this ecosystem. This is one of the first studies to describe the analysis of 23 individual OH-PAHs in fish bile, using authentic standards.

Human and crab exposure to mercury in the Caribbean coastal shoreline of Colombia: impact from an abandoned chlor-alkali plant.

Human hair samples from male and female people aged 6-85 years, as well as muscle of crabs (Callinectes sapidus and Callinectes bocourti) were collected from different fishing places along the Caribbean coastal shoreline of Colombia and analyzed for total mercury (T-Hg) in order to establish the impact of mercury-polluted sediments in Cartagena bay on the ecosystem. Hair T-Hg in inhabitants varied between 0.1 and 21.8 microg/g, with average and median of 1.52 microg/g and 1.1 microg/g, respectively. Differences between sampling locations were significant (P<0.01) and median values decreased in the order: Caño del Oro (1.5 microg/g)

Blood lead levels in children aged 5-9 years living in Cartagena, Colombia.

During June-August 2004, blood lead (BPb) levels and various hematological parameters were evaluated in children aged 5-9 years old at ten primary schools located in eight neighborhoods in Cartagena, Colombia. The schools selected for this study are attended mainly by children from families of low income. A total of 189 subjects participated in the survey. The arithmetic mean+/-standard error BPb level was 5.49+/-0.23 microg/dL (range<1.0-21.0 microg/dL). The geometric mean was 4.74 microg/dL (95% CI: 4.29-5.18). A proportion of the children (7.4%) had BPb levels above the US Centers for Disease Control and Prevention's threshold of concern (10 microg Pb/dL). BPb levels were correlated weakly, but significantly and positively, with red blood cell count (RBC), and negatively with child body size, age, mean corpuscular volume (MCV), and mean corpuscular hemoglobin (MCH). BPb levels did not differ significantly between boys and girls but significant differences were observed between neighborhoods (P<0.001). Activities such as metal melting-related processes and fishing net sinker production are the main sources of Pb exposure in Cartagena.

Perfluorooctanesulfonate and related fluorochemicals in biological samples from the north coast of Colombia.

Perfluorinated compounds are widespread pollutants of toxicological importance that have been detected in environmental matrices. However, little is known on their distribution in South America. In this study, distribution of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonate (PFHxS), and perfluorooctanesulfonamide (PFOSA) was determined in the bile of mullet, Mugil incilis, and in tissues of pelicans (Pelecanus occidentalis) collected from North Colombia. Analysis was performed by HPLC mass spectrometry after ion-pair extraction. PFOS was found in all bile samples and PFOA and PFHxS were detected at lower frequency. Average concentrations of PFOS, PFOA, and PFHxS in bile of fish from Cartagena Bay, an industrialized site, and Totumo marsh, a reference site, were 3673, 370, 489 and 713, 47.4, 1.27 ng/mL, respectively. PFOS concentrations in pelican organs decreased in the order of spleen>liver>lung>kidney>brain>heart>muscle. These results suggest, for the first time, that perfluorinated compounds are also found in wildlife from Latin American countries.