Drugs of abuse and benzodiazepines in the Madrid Region (Central Spain): Seasonal variation in river waters,occurrence in tap water and potential environmental and human risk

This work analyzes the seasonal variation (winter and summer) of ten drugs of abuse, six metabolites and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain. The occurrence of these compounds in tap water in this region is also investigated and a preliminary human health risk characterization performed for those substances found in tap water. Finally, a screening level risk assessment that combines the measured environmental concentrations (MECs) with dose–response data to estimate Hazard Quotients (HQs) for the compounds studied is also presented.The results of this study show the presence of fourteen out of the nineteen compounds analyzed in winter and twelve of them in summer. The most ubiquitous compounds, with a frequency of detection of 100% in both seasons, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-type stimulant (ATS) ephedrine (EPH), the opioid methadone (METH), the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three benzodiazepines investigated, namely alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). The highest concentrations observed corresponded to EPH (1020 ng L^− 1 in winter and 250 ng L^− 1 in summer). The only compounds not detected in both seasons were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (O-H-LSD), and Δ⁹-tetrahydrocannabinol (THC). In terms of overall concentration, all sampling points presented higher concentrations in winter than in summer. Statistical analyses performed to gather evidence concerning occasional seasonal differences in the concentrations of individual substances between summer and winter showed statistically significantly higher concentrations (p < 0.05) of BE, EPH and the opioid morphine (MOR) in winter than in summer. Two out of the nineteen compounds studied, namely cocaine (CO) and EPH, were detected in tap water from one sampling point at concentrations of 1.61 and 0.29 ng L^− 1, respectively. The preliminary human health risk characterization showed that no toxic effects could be expected at the detected concentration level in tap water.The screening level risk assessment showed that MOR, EDDP and the THC metabolite 11-nor-9-carboxy-Δ⁹-tetrahydrocannabinol (THC-COOH) were present in at least one of the sampling sites in a concentration leading to a Hazard Quotient (HQ) value between 1.0 and 10.0, thus indicating some possible adverse effects. The cumulative HQ or Toxic units (TUs) calculated for each of the groups studied showed that opioids and cannabinoids were present at concentrations high enough to potentially generate some adverse effects on at least one sampling point.     

Refining the excretion factors of methadone and codeine for wastewater analysis — Combining data from pharmacokinetic and wastewater studies

Analysing drug residues in wastewater (wastewater analysis) to monitor the consumption of those drugs in the population has become a complementary method to epidemiological surveys. In this method, the excretion factor of a drug (or the percentage of drug metabolites excreted through urine) is a critical parameter for the back-estimation of the consumption of a drug. However, this parameter is usually derived from a small database of human pharmacokinetic studies. This is true for methadone and codeine, the two most commonly used opioids and also common substances of abuse. Therefore, we aimed to refine the current excretion factors used for estimating methadone and codeine by analysing published data from the literature on the excretion of methadone, its main metabolite, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and codeine. Our review included both human drug pharmacokinetic studies and wastewater analysis studies. We found that while the commonly used excretion factor of methadone (~ 27.5%) was relatively accurate, the excretion factor of EDDP, a better biomarker for methadone consumption in sewer epidemiology, should be twice that of methadone (i.e. 55%) instead of the current equal or half values. For codeine, the excretion factor should be ~ 30% instead of 63.5% or 10% as previously used in wastewater analysis studies. Data from wastewater analysis studies could be used in this way to refine the excretion factors of the drugs of interest.     

Determination of non-steroidal anti-inflammatory drug (NSAIDs) residues in water samples

Pharmacologically active substances used to treat human and animal illnesses can enter the aquatic environment via effluents from wastewater treatment plants or in the case of veterinary drugs directly through liquid manure discharge. Some of these substances enter the environment either as the parent compound or as active/inactive metabolites. Due to their pharmacological activity, their determination and understanding their behavior and fate in the environment are important. The scope of this paper was to develop an analytical procedure to determine common pharmaceutical residues in wastewaters. Pharmacologically active substances were chosen according to their wide spread application in Slovenia and Central Europe and are members of analgesics, e.g., non-steroidal anti-inflammatory drugs: ibuprofen, naproxen, ketoprofen and diclofenac. Selected compounds were isolated from synthetic water using a novel SPE sorbent Strata X. Due to the non-volatile nature of these compounds they were first silylised prior to gas chromatographic-mass spectrometric detection. The developed procedure was tested with synthetic wastewaters and their extraction efficiency (>84%) and method limits of detection (2-6 ng L(-1)) were determined. Our procedure has been adopted and optimised for "real" water samples and applied to eleven drinking and ten river water samples from Slovenia. The results showed no traces of NSAIDs in all potable water samples and low-range contamination (ng L(-1)) of Slovene rivers. These results show that NSAIDs contamination of Slovene waters is comparable with published results of water contamination in Central Europe.     

Radionuclide and chemical concentrations in mineral waters at Saratoga Springs, New York

A project to characterize the radionuclide and chemical components in natural spring waters in the vicinity of Saratoga Springs, New York (USA) has been completed. As a result of the measured radionuclide and chemical content, eight springs were labeled as mineral waters, whereas three springs contained very low concentrations of these components. The mineral waters were highly enriched in alkaline and alkaline-earth elements, as well as chloride ions. Three isotopes of radium ((224)Ra, (226)Ra, (228)Ra) were detected in the mineral waters and reached concentrations of 1, 20, and 2 Bq/L, respectively. Overall, the (226)Ra isotope constituted about 80% of the total radioactivity measured in the water samples. Dissolved uranium concentrations in the mineral waters were very low (mean approximately 50 mBq/L).     

Exploring the fate,transport and risk of Perfluorooctane Sulfonate (PFOS) in a coastal region of China using a multimedia model

Perfluorooctane Sulfonate (PFOS) and related substances have been widely applied in both industrial processes and domestic products in China. Exploring the environmental fate and transport of PFOS using modeling methods provides an important link between emission and multimedia diffusion which forms a vital part in the human health risk assessment and chemical management for these substances. In this study, the gridded fugacity based BETR model was modified to make it more suitable to model transfer processes of PFOS in a coastal region, including changes to PFOS partition coefficients to reflect the influence of water salinity on its sorption behavior. The fate and transport of PFOS in the Bohai coastal region of China were simulated under steady state with the modified version of the model. Spatially distributed emissions of PFOS and related substances in 2010 were estimated and used in these simulations. Four different emission scenarios were investigated, in which a range of half-lives for PFOS related substances were considered. Concentrations of PFOS in air, vegetation, soil, fresh water, fresh water sediment and coastal water were derived from the model under the steady-state assumption. The median modeled PFOS concentrations in fresh water, fresh water sediment and soil were 7.20 ng/L, 0.39 ng/g and 0.21 ng/g, respectively, under Emission Scenario 2 (which assumed all PFOS related substances immediately degrade to PFOS) for the whole region, while the maximum concentrations were 47.10 ng/L, 4.98 ng/g and 2.49 ng/g, respectively. Measured concentration data for PFOS in the Bohai coastal region around the year of 2010 were collected from the literature. The reliability of the model results was evaluated by comparing the range of modeled concentrations with the measured data, which generally matched well for the main compartments. Fate and transfer fluxes were derived from the model based on the calculated inventory within the compartments, transfer fluxes between compartments and advection fluxes between sub-regions. It showed that soil and costal water were likely to be the most important sinks of PFOS in the Bohai costal region, in which more than 90% of PFOS was stored. Flows of fresh water were the driving force for spatial transport of PFOS in this region. Influences of the seasonal change of fresh water fluxes on the model results were also analyzed. When only seasonal changes of the fresh water flow rates were considered, concentrations of PFOS in winter and spring were predicted to be higher than that under annual average conditions, while the concentrations in summer and autumn were lower. For PFOS fluxes entering the sea, opposite conclusions were drawn compared to the concentrations. Environmental risks from the presence of PFOS in fresh water were assessed for this region through comparison with available water quality criteria values. The predicted concentrations of PFOS in the Bohai coastal region provided by the model were lower than the water quality criteria published by the United States Environmental Protection Agency and Chinese researchers, while the concentrations in more than 80% of the sampling locations exceeded the European Union Water Framework Directive Environmental Quality Standards values. Seasonal variations of flow rate might cause a significant increase in environmental risks.     

Cocaine and cannabinoids in the atmosphere of Northern Europe cities,comparison with Southern Europe and wastewater analysis

This study reports the first investigation of atmospheric illicit drug concentrations in Northern Europe using measurements of cocaine and cannabinoids in Amsterdam, London and Stockholm. Further, these measurements were compared to those made in Rome to explore the geographical and inter-city variability. Co-located measurements of atmospheric particulate mass and PAHs were used to help describe and interpret the illicit drug measurements with respect to atmospheric dispersion. Cocaine concentrations ranged from 0.03 to 0.14 ng/m³ in Amsterdam, from 0.02 to 0.33 ng/m³ in London and were below quantification limit (3 pg/m³) in Stockholm. Cannabinol was the only cannabinoid molecule detected in the three cities. During this campaign, London reported the highest concentrations of cocaine and meaningful differences were detected between the urban background and city centre London sites. Mean cocaine concentrations measured in Amsterdam during March 2011 were also compared with those measured simultaneously in eight Italian cities. The cocaine concentration in Amsterdam was comparable to that measured at an urban background in Milan and at a densely populated site in Florence. Although correlating atmospheric concentrations directly with drug prevalence is not possible using current data, links between concentrations of cocaine and estimates of abuse prevalence assessed by the more routinely used wastewater analysis were also examined. A statistically significant correlation was found between the two sets of data (R² = 0.66; p = 0.00131). Results confirmed that meteorology, population rate and habits of consumption influence the atmospheric concentrations of drugs. If these confounding factors were better controlled for, the techniques described here could became an easy and cost effective tool to index the impact of cocaine abuse in the area; especially where local hot spots need to be identified.     

Occurrence of sulfonamide residues along the Ebro River basin: removal in wastewater treatment plants and environmental impact assessment

Sulfonamides (SAs) have become one of the antibiotic families most frequently found in all kind of environmental waters. In the present work, the presence of 16 SAs and one of their acetylated metabolites in different water matrices of the Ebro River basin has been evaluated during two different sampling campaigns carried out in 2007 and 2008. Influent and effluent samples from seven wastewater treatment plants (WWTPs), together with a total of 28 river water samples were analyzed by on-line solid phase extraction-liquid chromathography-tandem mass spectrometry (on-line SPE-LC-MS/MS). Sulfamethoxazole and sulfapyridine were the SAs most frequently detected in WWTPs (96-100%), showing also the highest concentrations, ranging from 27.2 ng L(-1) to 596 ng L(-1) for sulfamethoxazole and from 3.7 ng L(-1) to 227 ng L(-1) for sulfapyridine. Sulfamethoxazole was also the SA most frequently detected in surface waters (85% of the samples) at concentrations between 11 ng L(-1) and 112 ng L(-1). In order to assess the effectiveness of the wastewater treatment in degrading SAs, removal efficiencies in the seven WWTPs were calculated for each individual SA (ranging from 4% to 100%) and correlated to the corresponding hydraulic retention times or residence times of the SAs in the plants. SAs half-lives were also estimated, ranging from to 2.5 hours (sulfadimethoxine) to 128 h (sulfamethazine). The contribution of the WWTPs to the presence of SAs depends on both the load of SAs discharging on the surface water from the WWTP effluent but also on the flow of the receiving waters in the discharge sites and the dilution exerted; WWTP4 exerts the highest pressure on the receiving water course. Finally, the potential environmental risk posed by SAs was evaluated calculating the hazard quotients (HQ) to different non-target organisms in effluent and river water. The degree of susceptibility resulted in algae>daphnia>fish. Sulfamethoxazole was the only SA posing a risk to algae in effluent water, with an HQ>7.     

Health risks from large-scale water pollution: trends in Central Asia

Limited data on the pollution status of spatially extensive water systems constrain health-risk assessments at basin-scales. Using a recipient measurement approach in a terminal water body, we show that agricultural and industrial pollutants in groundwater-surface water systems of the Aral Sea Drainage Basin (covering the main part of Central Asia) yield cumulative health hazards above guideline values in downstream surface waters, due to high concentrations of copper, arsenic, nitrite, and to certain extent dichlorodiphenyltrichloroethane (DDT). Considering these high-impact contaminants, we furthermore perform trend analyses of their upstream spatial-temporal distribution, investigating dominant large-scale spreading mechanisms. The ratio between parent DDT and its degradation products showed that discharges into or depositions onto surface waters are likely to be recent or ongoing. In river water, copper concentrations peak during the spring season, after thawing and snow melt. High spatial variability of arsenic concentrations in river water could reflect its local presence in the top soil of nearby agricultural fields. Overall, groundwaters were associated with much higher health risks than surface waters. Health risks can therefore increase considerably, if the downstream population must switch to groundwater-based drinking water supplies during surface water shortage. Arid regions are generally vulnerable to this problem due to ongoing irrigation expansion and climate changes.     

Occurrence and distribution of organochlorine pesticides - lindane, p,p'-DDT, and heptachlor epoxide - in surface water of China

Persistent organochlorine pesticides pollutants (OCPs) have been reported to occur at relatively high concentrations in some Chinese waters. In order to map the distribution of organochlorine pesticides in the surface water throughout China, samples were collected from over 600 sites in seven major river basins and three main internal rivers drainage areas during 2003 and 2004. The surface water samples were analyzed for the representative organochlorine pesticides contaminants including lindane (gamma-HCH), p,p'-DDT and heptachlor epoxide. In general, the most frequently detected compound was lindane, being detected in 83.9% of samples (mean=31.3 ng/l; range <0.17-860 ng/l), and the highest concentration was present in the Yellow River basin. p,p'-DDT was detected in 63.1% of the samples collected (mean=14.6 ng/l; range <0.14-368 ng/l) with the highest concentration present in the Huaihe River basin. Heptachlor epoxide was detected in only 9.3% of water samples (range <0.11-10 ng/l). Measured concentrations for the three compounds were low and rarely exceed the environment quality standard for surface water of China. Lindane was more frequently detected at much higher concentrations in the rivers of northern China compared with those of southern China. The sites with higher concentration of lindane and p,p'-DDT mainly occurred in the Yellow River and Huaihe River basins, so the results of this investigation indicate that the organochlorine pesticide contamination of Yellow River and Huaihe River basins should be of particular concern relative to the other basins. When compared with other regions of the world, it appears that the Chinese surface water is moderately polluted by lindane and p,p'-DDT.     

Refined sewer epidemiology mass balances and their application to heroin, cocaine and ecstasy

The detection of illicit drugs in environmental matrices may be a cause for concern, both from the perspective of their potential environmental impacts and the fact that their presence in detectable concentrations would be an indicator of significant drug use. The primary goal behind recent studies on this subject has been to use measured influent concentrations of selected illicit drugs or their in vivo metabolites in the environment as a means of estimating the abuse level of these drugs and patterns of consumption. Thus-far, such calculations have hinged on the use of solitary excretion estimates from single studies of limited scope and/or studies of limited applicability. Therefore, the need exists to conduct a comprehensive meta-analysis of metabolic disposition studies to construct excretions profiles for the various illicit drugs and their in vivo metabolites. The constructed excretory profiles should not only provide mean excretion values but also indicate the expected variations in excreted fractions that arise due to differences not only in the metabolic capacity of users but also in the efficiencies of various routes of administration for a given illicit drug. Therefore, the primary goal of the research presented here was to refine sewer epidemiology extrapolation mass balances for various illicit drugs of interest by constructing their excretory profiles segregated by route-of-administration. After conducting such a study with a multi-national scope on illicit drugs including cocaine, heroin and ecstasy, the results obtained clearly indicate that extrapolation factors currently being used in literature for these drugs to enumerate prevalence of abuse required significant refinement to increase their reliability.     

PCB levels in surface and waste waters in Egypt

Samples of surface water from the river Nile, Ismailia and El-Mahmodia Canals, and waste waters from eight plants were collected and analysed for determination of PCB levels. The mean concentrations of PCBs in River Nile, Ismailia Canal, El-Mahmodia Canal, and waste waters were 24 ± 14, 39 ± 18, and 170 ± 150 ng/L, respectively. The waste waters discharged from industrial plants were found to increase the levels of PCBs in surface waters. The concentrations of PCBs in the River Nile and two Canals are within the range found in the Hudson, Avon, and Frome Rivers, and for the Northern Mississippi area.     

The Water Regime of Black Saxaul in Various Environmental Conditions of the Central Asian Desert

A water regime, estimated based on transpiration rate, water content of shoots, concentration of cell sap, and water consumption per unit area, was studied for black saxaul. The seasonal course of black saxaul transpiration during the growing season increased by the middle of summer (July) and decreased towards autumn. The highest transpiration rate of black saxaul was found in Karnabchul, where ground waters poorly mineralized, located at a depth of 14–20 m in nonsaline soils. The lowest transpiration rate was detected in the Nishan “steppe,” where ground waters were also located at 14–20 m, however they were highly mineralized, and the soil profile was highly salinated. The Southwestern Kyzylkum, characterized by ground waters at a very deep location (more than 100 m) and low soil salinity, occupied an intermediate position in terms of transpiration rate. The maximal water consumption for transpiration during the vegetation period was observed in Karnabchulat 642.5 mm/ha, then in the Nishan “steppe” at 352.5. The minimal value was detected in the Southwestern Kyzylkum at 171.0.

     

239,240Pu, 241Am and 232Th in lakes: The effects of seasonal anoxia

A pond which undergoes seasonal anoxia as a result of thermal stratification was studied to assess the possible release of actinide elements from anoxic sediments to the pond waters. Concentration profiles of ^239,240Pu, ²⁴¹Am, ²³²Th, iron and manganese in the water column show significant increases in concentration for all elements in the anoxic deep waters. However, calculated total inventories of the elements in the pond water indicate no apparent input of actinide elements to the system during summer stratification. Similar inventory calculations for ^239,240Pu in a previously studied system support the results of this study. The lack of a significant increase in pond inventories of actinide elements coupled with a lack of correspondence of concentration profiles of the actinide elements to the seasonal Fe and Mn concentrations profiles argues that the increases in concentrations observed for these elements in anoxic bottom waters result from the downward transport of material already in the water column rather than release from the sediments.     

Human recreational exposure to antibiotic resistant bacteria in coastal bathing waters

Infections caused by antibiotic resistant bacteria (ARB) are associated with poor health outcomes and are recognised globally as a serious health problem. Much research has been conducted on the transmission of ARB to humans. Yet the role the natural environment plays in the spread of ARB and antibiotic resistance genes is not well understood. Antibiotic resistant bacteria have been detected in natural aquatic environments, and ingestion of seawater during water sports is one route by which many people could be directly exposed.The aim was to estimate the prevalence of resistance to one clinically important class of antibiotics (third-generation cephalosporins (3GCs)) amongst Escherichia coli in coastal surface waters in England and Wales. Prevalence data was used to quantify ingestion of 3GC-resistant E. coli (3GCREC) by people participating in water sports in designated coastal bathing waters. A further aim was to use this value to derive a population-level estimate of exposure to these bacteria during recreational use of coastal waters in 2012.The prevalence of 3GC-resistance amongst E. coli isolated from coastal surface waters was estimated using culture-based methods. This was combined with the density of E. coli reported in designated coastal bathing waters along with estimations of the volumes of water ingested during various water sports reported in the literature to calculate the mean number of 3GCREC ingested during different water sports.0.12% of E. coli isolated from surface waters were resistant to 3GCs. This value was used to estimate that in England and Wales over 6.3 million water sport sessions occurred in 2012 that resulted in the ingestion of at least one 3GCREC.Despite the low prevalence of resistance to 3GCs amongst E. coli in surface waters, there is an identifiable human exposure risk for water users, which varies with the type of water sport undertaken. The relative importance of this exposure is likely to be greater in areas where a large proportion of the population enjoys water sports. Millions of water sport sessions occurred in 2012 that were likely to have resulted in people ingesting E. coli resistant to a single class of antibiotics (3GCs). However, this is expected to be a significant underestimate of recreational exposure to all ARB in seawater.This is the first study to use volumes of water ingested during different water sports to estimate human exposure to ARB. Further work needs to be done to elucidate the health implications and clinical relevance of exposure to ARB in both marine and fresh waters in order to fully understand the risk to public health.     

Petroleum residues in the waters of the Shatt al-Arab River and the northwest region of the Arabian Gulf

During April 1980, water samples were collected from 12 sites in the Shatt al-Arab River and its estuary in the northwest region of the Arabian Gulf. The samples were extracted and the concentration of petroleum hydrocarbons were determined spectrofluorometrically, in order to provide information on the background values of oil generally present in these waters. Total hydrocarbon concentrations of these samples ranged from 2.7 to 86.7 μgL^?1 expressed in terms of Kuwait crude oil equivalents. The highest concentrations were found at sites in the Shatt al-Arab River that are near port areas.     

鄱阳湖蝶形湖泊水体氮磷等的变化及污染初步评价

分别于2014年夏季7月和冬季12月对鄱阳湖蝶形水域的9个湖泊进行了采样,并对湖泊水质基础性指标TN、TP、NH_3-N、NO_3~--N、NO_2~--N、溶解性磷酸盐、TOC、COD_(Mn)和叶绿素a进行了测定与分析。据此同时运用单因素评价法、均值型指数综合评价法和营养状态指数法对鄱阳湖蝶形水域的地表水水环境的污染现状和污染程度进行了评价,以更全面和准确地反映鄱阳湖蝶形水域的水质状况。结果显示:(1)鄱阳湖蝶形水域水质总体符合GB3838-2002III类水标准;(2)7月水质总体优于12月水质。12月总氮含量和总磷含量基本都高于7月,叶绿素a含量除中湖池12月值略低于7月外,其它点位12月值均高于7月。7月总氮值为0.6~1.3 mg/L,总磷值为0.02~0.15 mg/L,叶绿素a为2.2~6.7 mg/L;12月总氮值为0.6~2.0 mg/L,总磷值为0.04~0.19 mg/L,叶绿素a为3.8~34.7 mg/L;(3)7月和12月水质营养状态介于中营养和轻度富营养,水体主要污染物质为总氮和总磷。7月蚌湖营养状态为轻度富营养,其它点位为中营养,12月除常湖、梅溪湖和大汊湖营养状态为中营养,其它点位均为轻度富营养;(4)位于南部的象湖、常湖、白沙湖和大汊湖水质整体较其它蝶形湖泊差,主要是受到工业废水、生活污水和农业面源污染的赣江和饶河的污染输入影响所致。基于以上调查测试结果提出保护和改善鄱阳湖水环境的可行性措施,以促进鄱阳湖蝶形水域水资源的开发利用,实现经济与环境及资源的协调可持续发展。     

Phytoestrogens and mycoestrogens in surface waters — Their sources,occurrence, and potential contribution to estrogenic activity

This review discusses the potential contribution of phytoestrogens and mycoestrogens to in vitro estrogenic activities occurring in surface waters and in vivo estrogenic effects in fish. Main types, sources, and pathways of entry into aquatic environment of these detected compounds were summarized. Reviewed concentrations of phyto/mycoestrogens in surface waters were mostly undetectable or in low ng/L ranges, but exceeded tens of μg/L for the flavonoids biochanin A, daidzein and genistein at some sites. While a few phytosterols were reported to occur at relatively high concentrations in surface waters, information about their potencies in in vitro systems is very limited, and contradictory in some cases. The relative estrogenic activities of compounds (compared to standard estrogen 17β-estradiol) by various in vitro assays were included, and found to differ by orders of magnitude. These potencies were used to estimate total potential estrogenic activities based on chemical analyses of phyto/mycoestrogens. In vivo effective concentrations of waterborne phyto/mycoestrogens were available only for biochanin A, daidzein, formononetin, genistein, equol, sitosterol, and zearalenone. The lowest observable effect concentrations in vivo were reported for the mycoestrogen zearalenone. This compound and especially its metabolites also elicited the highest in vitro estrogenic potencies. Despite the limited information available, the review documents low contribution of phyto/mycoestrogens to estrogenic activity in vast majority of surface waters, but significant contribution to in vitro responses and potentially also to in vivo effects in areas with high concentrations.     

Americium,plutonium and uranium contamination and speciation in well waters,streams and atomic lakes in the Sarzhal region of the Semipalatinsk Nuclear Test Site,Kazakhstan

New data are reported on the concentrations, isotopic composition and speciation of americium, plutonium and uranium in surface and ground waters in the Sarzhal region of the Semipalatinsk Test Site, and an adjacent area including the settlement of Sarzhal. The data relate to filtered water and suspended particulate from (a) streams originating in the Degelen Mountains, (b) the Tel′kem 1 and Tel′kem 2 atomic craters, and (c) wells on farms located within the study area and at Sarzhal. The measurements show that ²⁴¹Am, ^239,240Pu and ²³⁸U concentrations in well waters within the study area are in the range 0.04–87 mBq dm⁻³, 0.7–99 mBq dm⁻³, and 74–213 mBq dm⁻³, respectively, and for ²⁴¹Am and ^239,240Pu are elevated above the levels expected solely on the basis of global fallout. Concentrations in streams sourced in the Degelen Mountains are similar, while concentrations in the two water-filled atomic craters are somewhat higher. Suspended particulate concentrations in well waters vary considerably, though median values are very low, at 0.01 mBq dm⁻³, 0.08 mBq dm⁻³ and 0.32 mBq dm⁻³ for ²⁴¹Am, ^239,240Pu and ²³⁸U, respectively. The ²³⁵U/²³⁸U isotopic ratio in almost all well and stream waters is slightly elevated above the ‘best estimate’ value for natural uranium worldwide, suggesting that some of the uranium in these waters is of test-site provenance. Redox analysis shows that on average most of the plutonium present in the microfiltered fraction of these waters is in a chemically reduced form (mean 69%; 95% confidence interval 53–85%). In the case of the atomic craters, the proportion is even higher. As expected, all of the americium present appears to be in a reduced form. Calculations suggest that annual committed effective doses to individual adults arising from the daily ingestion of these well waters are in the range 11–42 μSv (mean 21 μSv). Presently, the ground water feeding these wells would not appear to be contaminated with radioactivity from past underground testing in the Degelen Mountains or from the Tel′kem explosions.     

Speciation patterns of actinides in natural waters: a laboratory investigation

The results of laboratory investigations of actinide speciation in ground waters of varying compositions are summarized, re-evaluated and further interpreted, with the inclusion of additional data. Actinide speciation (solubility, oxidation state distributions) in these water samples exhibits great variability at 10⁻¹⁰ to 10⁻⁸ M total actinide concentrations. Americium solubility appears to be controlled by the formation of radiocolloids. neptunium is predictably oxidized and soluble in these water samples, with only a few exceptions. Plutonium exhibits widely varying oxidation state distributions—and hence solubility— despite the presence of 6 mg liter⁻¹ dissolved oxygen in all experiments. Plutonium solubility is enhanced by carbonate and fluoride but is diminished by sulfate in reducing waters. In general, these results are compatible with the limited information available for actinide speciation from previous in-situ investigations but they emphasize the paucity of accurate thermodynamic data to describe these systems.     

Abnormal high natural radium concentration in surface waters

Unexpected high 228Ra concentrations, up to 2 Bq 1(-1), were found in waters of a coastal lagoon close to a monazite sand separation plant. Due to their use as process waters in this plant, the initial supposition was a contamination related to its operation. However, it was concluded that these abnormal radium concentrations had a natural origin, springs at the lagoon head area with high 228Ra and 226Ra concentrations. The strong relationship among radium and light rare-earth elements (LREEs), the observed 228Ra/226Ra activity ratio and the rare-earth element pattern in the spring waters suggested that monazite is the main source of nuclides for water, indicating the disturbance of monazite chemical stability by the combined effects of low pH and high salinity. Both factors combined allow relatively low mobility of thorium, but, on the other hand, a relatively high mobility of radium and LREEs.