Reactions of hypobromous acid with dimethyl selenide, dimethyl diselenide and other organic selenium compounds: kinetics and product formation.

Selenium (Se) is an essential micronutrient for many living organisms particularly due to its unique redox properties. We recently found that the sulfur (S) analog for dimethyl selenide (DMSe), i.e. dimethyl sulfide (DMS), reacts fast with the marine oxidant hypobromous acid (HOBr) which likely serves as a sink of marine DMS. Here we investigated the reactivity of HOBr with dimethyl selenide and dimethyl diselenide (DMDSe), which are the main volatile Se compounds biogenically produced in marine waters. In addition, the reactivity of HOBr with further organic Se compounds was tested, i.e., SeMet (as N-acetylated-SeMet), and selenocystine (SeCys2 as N-acetylated-SeCys2), as well as the phenyl-analogs of DMSe and DMDSe, respectively, diphenyl selenide (DPSe) and diphenyl diselenide (DPDSe). Apparent second-order rate constants at pH 8 for the reactions of HOBr with the studied Se compounds were (7.1 ± 0.7) × 107 M-1 s-1 for DMSe, (4.3 ± 0.4) × 107 M-1 s-1 for DMDSe, (2.8 ± 0.3) × 108 M-1 s-1 for SeMet, (3.8 ± 0.2) × 107 M-1 s-1 for SeCys2, (3.5 ± 0.1) × 107 M-1 s-1 for DPSe, and (8.0 ± 0.4) × 106 M-1 s-1 for DPDSe, indicating a very high reactivity of all selected Se compounds with HOBr. The reactivity between HOBr and DMSe is lower than for DMS and therefore this reaction is likely not relevant for marine DMSe abatement. However, the high reactivity of SeMet with HOBr suggests that SeMet may act as a relevant quencher of HOBr.

Geochemical Soil Atlas of Switzerland - Distribution of Toxic Elements.

Chemical elements such as copper and molybdenum are essential for animal and human health but may become toxic at elevated concentrations depending on the exposure and intake rate. Other elements such as mercury pose a threat to human health at already low concentrations. The soil acts as the main source of these elements for plant uptake and is thus driving accumulation along the food chain. However, in Switzerland, no nationwide information on elemental distributions in soils has existed up to now. The geochemical soil atlas of Switzerland will fill this gap by presenting the concentration ranges and the spatial distribution of 20 elements in the topsoil. In this summary, we present the methodological approaches and some main findings of the atlas with a focus on toxic elements as well as elements that can be or are toxic at higher concentrations.

Sensitive analysis of selenium speciation in natural seawater by isotope-dilution and large volume injection using PTV-GC-ICP-MS.

Although oceans play a key role in the global selenium (Se) cycle, there is currently very little quantitative information available on the distribution of Se concentrations and Se speciation in marine environments. In general, determining Se concentration and speciation in seawater is highly challenging due to very low Se levels ((sub)ng⋅L-1), whereas matrix elements interfering Se pre-concentration and detection are up to the g⋅L-1 levels. In this study, we established a sensitive method for the determination of the various Se chemical fractions present in natural seawater, i.e. selenite (SeIV), selenate (SeVI), organic Se-II + Se0 and total Se, using species-specific isotope dilution gas chromatography coupled to inductively coupled plasma mass spectrometry (ID-GC-ICP-MS). We compared different derivatization reagents and optimized specific pre-treatment protocols, including a microwave assisted oxidation protocol for the determination of total Se and organic Se-II + Se0 using H2O2. To increase sensitivity, we developed an online pre-concentration method based on large volume injection (LVI) using a programmed temperature vaporization (PTV) inlet. Eventually, the developed method achieved low absolute and methodological detection limits, i.e., respectively, 0.1-0.3 pg and 0.9-3.1 ng.L-1 for the different fractions. The accuracy of our method was of 2% for a certified reference material (CRM) diluted in artificial seawater while the precision was better than 4% for a freshwater CRM in artificial seawater matrix as well as two common seawater CRMs certified for trace elements excluding Se. As a proof-of-concept, we quantified the various Se fractions in a large number of natural water samples from the Baltic and North Seas, encompassing a wide range of salinity (7-35 psu), which shows that its detection limits are sufficient to determine total Se, SeIV, SeVI and organic Se-II + Se0 concentrations in brackish and marine systems.

Sensitive and High-Throughput Analysis of Volatile Organic Species of S, Se, Br, and I at Trace Levels in Water and Atmospheric Samples by Thermal Desorption Coupled to Gas Chromatography and Inductively Coupled Plasma Mass Spectrometry.

Emissions of volatile organic sulfur (S), selenium (Se), bromine (Br), and iodine (I) species from aquatic ecosystems represent an important source of these elements into the atmosphere. Available methods to measure these species are either not sensitive enough or not automated, which hinder a full understanding of species distribution and production mechanisms. Here, we present a sensitive and high-throughput method for the simultaneous and comprehensive quantification of S, Se, Br, and I volatile organic species in atmospheric and aqueous samples using a preconcentration step onto sorbent tubes and subsequent analysis by thermal desorption coupled to gas chromatography and inductively coupled plasma mass spectrometry (TD-GC-ICP-MS). Selected commercially available sorbent tubes, consisting of mixed porous polymer and graphitized black carbon, offered the highest trapping capacity and lowest loss of species when stored at -20 °C for 28 days after sampling. After optimization of the TD-GC-ICP-MS method, absolute detection limits were better than 3.8 pg, 9.1 fg, 313 fg, and 50 fg, respectively, for S, Se, Br, and I species. As a proof of concept, the concentrations of target species were determined in aqueous and continuously collected atmospheric samples during a cruise in the Baltic and North Seas. Moreover, unknown S, Br, and I volatile species were detected in both aqueous and atmospheric samples demonstrating the full potential of the method.

Understanding soil selenium accumulation and bioavailability through size resolved and elemental characterization of soil extracts.

Dietary deficiency of selenium is a global health threat related to low selenium concentrations in crops. Despite the chemical similarity of selenium to the two more abundantly studied elements sulfur and arsenic, the understanding of its accumulation in soils and availability for plants is limited. The lack of understanding of soil selenium cycling is largely due to the unavailability of methods to characterize selenium species in soils, especially the organic ones. Here we develop a size-resolved multi-elemental method using liquid chromatography and elemental mass spectrometry, which enables an advanced characterization of selenium, sulfur, and arsenic species in soil extracts. We apply the analytical approach to soils sampled along the Kohala rainfall gradient on Big Island (Hawaii), which cover a large range of organic carbon and (oxy)hydroxides contents. Similarly to sulfur but contrarily to arsenic, a large fraction of selenium is found associated with organic matter in these soils. However, while sulfur and arsenic are predominantly found as oxyanions in water extracts, selenium mainly exists as small hydrophilic organic compounds. Combining Kohala soil speciation data with concentrations in parent rock and plants further suggests that selenium association with organic matter limits its mobility in soils and availability for plants.

Long-term preservation of biomolecules in lake sediments: potential importance of physical shielding by recalcitrant cell walls.

Even though lake sediments are globally important organic carbon (OC) sinks, the controls on long-term OC storage in these sediments are unclear. Using a multiproxy approach, we investigate changes in diatom, green algae, and vascular plant biomolecules in sedimentary records from the past centuries across five temperate lakes with different trophic histories. Despite past increases in the input and burial of OC in sediments of eutrophic lakes, biomolecule quantities in sediments of all lakes are primarily controlled by postburial microbial degradation over the time scales studied. We, moreover, observe major differences in biomolecule degradation patterns across diatoms, green algae, and vascular plants. Degradation rates of labile diatom DNA exceed those of chemically more resistant diatom lipids, suggesting that chemical reactivity mainly controls diatom biomolecule degradation rates in the lakes studied. By contrast, degradation rates of green algal and vascular plant DNA are significantly lower than those of diatom DNA, and in a similar range as corresponding, much less reactive lipid biomarkers and structural macromolecules, including lignin. We propose that physical shielding by degradation-resistant cell wall components, such as algaenan in green algae and lignin in vascular plants, contributes to the long-term preservation of labile biomolecules in both groups and significantly influences the long-term burial of OC in lake sediments.

Purple sulfur bacteria fix N2 via molybdenum-nitrogenase in a low molybdenum Proterozoic ocean analogue.

Biological N2 fixation was key to the expansion of life on early Earth. The N2-fixing microorganisms and the nitrogenase type used in the Proterozoic are unknown, although it has been proposed that the canonical molybdenum-nitrogenase was not used due to low molybdenum availability. We investigate N2 fixation in Lake Cadagno, an analogue system to the sulfidic Proterozoic continental margins, using a combination of biogeochemical, molecular and single cell techniques. In Lake Cadagno, purple sulfur bacteria (PSB) are responsible for high N2 fixation rates, to our knowledge providing the first direct evidence for PSB in situ N2 fixation. Surprisingly, no alternative nitrogenases are detectable, and N2 fixation is exclusively catalyzed by molybdenum-nitrogenase. Our results show that molybdenum-nitrogenase is functional at low molybdenum conditions in situ and that in contrast to previous beliefs, PSB may have driven N2 fixation in the Proterozoic ocean.

Carbon and methane cycling in arsenic-contaminated aquifers.

Geogenic arsenic (As) contamination of groundwater is a health threat to millions of people worldwide, particularly in alluvial regions of South and Southeast Asia. Mitigation measures are often hindered by high heterogeneities in As concentrations, the cause(s) of which are elusive. Here we used a comprehensive suite of stable isotope analyses and hydrogeochemical parameters to shed light on the mechanisms in a typical high-As Holocene aquifer near Hanoi where groundwater is advected to a low-As Pleistocene aquifer. Carbon isotope signatures (δ13C-CH4, δ13C-DOC, δ13C-DIC) provided evidence that fermentation, methanogenesis and methanotrophy are actively contributing to the As heterogeneity. Methanogenesis occurred concurrently where As levels are high (>200 µg/L) and DOC-enriched aquitard pore water infiltrates into the aquifer. Along the flowpath to the Holocene/Pleistocene aquifer transition, methane oxidation causes a strong shift in δ13C-CH4 from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers.

Reaction of DMS and HOBr as a Sink for Marine DMS and an Inhibitor of Bromoform Formation.

Recently, we suggested that hypobromous acid (HOBr) is a sink for the marine volatile organic sulfur compound dimethyl sulfide (DMS). However, HOBr is also known to react with reactive moieties of dissolved organic matter (DOM) such as phenolic compounds to form bromoform (CHBr3) and other brominated compounds. The reaction between HOBr and DMS may thus compete with the reaction between HOBr and DOM. To study this potential competition, kinetic batch and diffusion-reactor experiments with DMS, HOBr, and DOM were performed. Based on the reaction kinetics, we modeled concentrations of DMS, HOBr, and CHBr3 during typical algal bloom fluxes of DMS and HOBr (10-13 to 10-9 M s-1). For an intermediate to high HOBr flux (≥10-11 M s-1) and a DMS flux ≤10-11 M s-1, the model shows that the DMS degradation by HOBr was higher than for photochemical oxidation, biological consumption, and sea-air gas exchange combined. For HOBr fluxes ≤10-11 M s-1 and a DMS flux of 10-11 M s-1, our model shows that CHBr3 decreases by 86% compared to a lower DMS flux of 10-12 M s-1. Therefore, the reaction between HOBr and DMS likely not only presents a sink for DMS but also may lead to suppressed CHBr3 formation.

Quantification of individual Rare Earth Elements from industrial sources in sewage sludge.

Rare Earth Elements (REEs) are used in increasing amounts in technical applications and consumer products. However, to date, the contribution of industrial sources to the loads of individual REEs in wastewater streams have not been quantified. Here, we determine the REE contents in sludge collected from 63 wastewater treatment plants (WWTPs) across Switzerland. To quantify the industrial fraction of individual REEs in the sewage sludge, we develop two complementary approaches, based on REE ratios and REE pattern fitting. Unspecific (background) inputs, with REE patterns similar to the averaged REE pattern of soils collected across Switzerland, dominate the REE budget of most WWTPs. A few WWTPs receive significant REE inputs from specific industrial sources. Based on population equivalents of Switzerland, we estimate a total annual load of 4200 kg Cerium (Ce, 0.5 g Ce year-1 capita-1), with an industrial contribution of 2000 kg year-1. The latter agrees with estimates of probabilistic mass flow models for engineered nanoscale CeO2 particles discharged to the sewer network. About 7 kg year-1 of Samarium (Sm,total for Switzerland: 184 kg year-1 or 0.02 g Sm year-1 capita-1) and 3 kg year-1 of Europium (Eu,total for Switzerland: 44 kg year-1 or 0.005 g Eu year-1 capita-1) are assigned to industrial inputs from single WWTPs. Gadolinium (Gd) is used in the form of a stable complex as contrast agent in magnetic resonance imaging. Assuming 10% removal of Gd during wastewater treatment, we calculate an annual discharge of 90 kg of Gd from one individual WWTP to surface waters. WWTPs with exceptionally high industrial inputs of specific REEs warrant detailed investigations to identify the respective sources and to assess whether REE concentrations in effluents are elevated to the same degree.

Arsenic and Other Geogenic Contaminants in Groundwater - A Global Challenge.

Groundwater is a much safer and more dependable source of drinking water than surface water. However, natural (geogenic) hazardous elements can contaminate groundwater and lead to severe health problems in consumers. Arsenic concentrations exceeding the WHO drinking water guideline of 10 µg/L globally affect over 220 million people and can cause arsenicosis (skin lesions and cancers). Fluoride, while preventing caries at low concentrations, has detrimental effects when above the WHO drinking water guideline of 1.5 mg/L and puts several hundred million people at risk of dental and skeletal fluorosis. In this article, we report on the geochemistry and occurrence of arsenic and fluoride in groundwater and on the development of global and regional risk maps that help alert governments and water providers to take appropriate mitigation measures for the provision of safe drinking water. We then summarize research on the removal of arsenic and fluoride from drinking water, focusing on adapted technologies for water treatment. Finally, we discuss the applicability of various measures in a larger context and future challenges in reaching the goal of access to safe drinking water for all.

Constraining Atmospheric Selenium Emissions Using Observations, Global Modeling, and Bayesian Inference.

Selenium (Se) is an essential dietary element for humans and animals, and the atmosphere is an important source of Se to soils. However, estimates of global atmospheric Se fluxes are highly uncertain. To constrain these uncertainties, we use a global model of atmospheric Se cycling and a database of more than 600 sites where Se in aerosol has been measured. Applying Bayesian inference techniques, we determine the probability distributions of global Se emissions from the four major sources: anthropogenic activities, volcanoes, marine biosphere, and terrestrial biosphere. Between 29 and 36 Gg of Se are emitted to the atmosphere every year, doubling previous estimates of emissions. Using emission parameters optimized by aerosol network measurements, our model shows good agreement with the aerosol Se observations (R2 = 0.66), as well as with independent aerosol (0.59) and wet deposition measurements (0.57). Both model and measurements show a decline in Se over North America in the last two decades because of changes in technology and energy policy. Our results highlight the role of the ocean as a net atmospheric Se sink, with around 7 Gg yr-1 of Se transferred from land through the atmosphere. The constrained Se emissions represent a substantial step forward in understanding the global Se cycle.

Mercury loads and fluxes from wastewater: A nationwide survey in Switzerland.

Mercury (Hg) pollution threatens ecosystems and human health. Wastewater treatment plants (WWTPs) play a key role in limiting Hg discharges from wastewaters to rivers and lakes, but large-scale studies to estimate Hg loads and discharge at national levels are scarce. We assessed the concentration, flux, speciation, and removal of Hg in municipal wastewater throughout Switzerland by investigating 64 WWTPs in a pre-study and a subset of 28 WWTPs in the main study. We also studied the behavior and pathways of Hg along the various treatment steps in a state-of-the-art WWTP. The resulting dataset, representative of industrialized countries, provides an overview of (i) current Hg concentration ranges, (ii) average per capita loads, and (iii) wastewater Hg inputs into surface waters. The results allowed estimation of a total Hg (THg) load in Swiss wastewater of 130 ± 30 kg THg/year (15.7 mg/capita/y), of which 96 ± 4% is retained in sewage sludge. About 4.7 ± 0.5 kg THg/year (0.57 mg/capita/y) is discharged with the treated wastewater into surface waters. This corresponds to only 1.5-3% of the THg load carried by the major Swiss rivers, indicating that >95% of riverine Hg originates from other sources. Extrapolation to the population of Europe would yield a total amount of 11,700 kg THg/year in raw wastewater, with some 480 kg THg/year discharged to surface waters. Monomethyl mercury on average accounted for 0.23% of THg, and its fraction remained constant along the different treatment steps.

Spatial and temporal evolution of groundwater arsenic contamination in the Red River delta, Vietnam: Interplay of mobilisation and retardation processes.

Geogenic arsenic (As) contamination of groundwater poses a major threat to global health, particularly in Asia. To mitigate this exposure, groundwater is increasingly extracted from low-As Pleistocene aquifers. This, however, disturbs groundwater flow and potentially draws high-As groundwater into low-As aquifers. Here we report a detailed characterisation of the Van Phuc aquifer in the Red River Delta region, Vietnam, where high-As groundwater from a Holocene aquifer is being drawn into a low-As Pleistocene aquifer. This study includes data from eight years (2010-2017) of groundwater observations to develop an understanding of the spatial and temporal evolution of the redox status and groundwater hydrochemistry. Arsenic concentrations were highly variable (0.5-510 µg/L) over spatial scales of <200 m. Five hydro(geo)chemical zones (indicated as A to E) were identified in the aquifer, each associated with specific As mobilisation and retardation processes. At the riverbank (zone A), As is mobilised from freshly deposited sediments where Fe(III)-reducing conditions occur. Arsenic is then transported across the Holocene aquifer (zone B), where the vertical intrusion of evaporative water, likely enriched in dissolved organic matter, promotes methanogenic conditions and further release of As (zone C). In the redox transition zone at the boundary of the two aquifers (zone D), groundwater arsenic concentrations decrease by sorption and incorporations onto Fe(II) carbonates and Fe(II)/Fe(III) (oxyhydr)oxides under reducing conditions. The sorption/incorporation of As onto Fe(III) minerals at the redox transition and in the Mn(IV)-reducing Pleistocene aquifer (zone E) has consistently kept As concentrations below 10 µg/L for the studied period of 2010-2017, and the location of the redox transition zone does not appear to have propagated significantly. Yet, the largest temporal hydrochemical changes were found in the Pleistocene aquifer caused by groundwater advection from the Holocene aquifer. This is critical and calls for detailed investigations.

Hypobromous Acid as an Unaccounted Sink for Marine Dimethyl Sulfide?

Marine emissions of dimethyl sulfide (DMS) to the atmosphere play a fundamental role in the global sulfur (S) cycle and have important consequences for the Earth's radiative balance. In the ocean, DMS is mainly produced by marine algae and bacteria via cleavage of the precursor compound dimethylsulfoniopropionate (DMSP). Here, we studied the reaction between DMS and the strong oxidant hypobromous acid (HOBr), which is also produced by marine algae. Further, reactions between DMS oxidation products and HOBr were studied. The second-order rate constants were determined in competition kinetic experiments using sulfite as a competitor. In addition, we developed a new HPLC-ICP-MS/MS method to identify and quantify the oxidation products of DMS and related compounds. We found that HOBr reacts very fast with DMS to dimethyl sulfoxide (DMSO), with a second-order rate constant of 1.6 × 109 M-1 s-1, while the subsequent oxidation of DMSO to dimethyl sulfone (DMSO2) is much slower (0.4 M-1 s-1). Concentrations of DMSP, DMSO2, and methanesulfonic acid (MSA) did not decrease when exposed to excess concentrations of HOBr, implying that these S-containing compounds are not or only slightly reactive toward HOBr. A quantitative comparison of known DMS sinks shows that HOBr may be an important, hitherto neglected sink for marine DMS that needs to be considered in ocean-atmosphere chemistry models.

Photochemical Production of Sulfate and Methanesulfonic Acid from Dissolved Organic Sulfur.

Photodegradation processes play an important role in releasing elements tied up in biologically refractory forms in the environment, and are increasingly being recognized as important contributors to biogeochemical cycles. While complete photo-oxidation of dissolved organic carbon (to CO2) and dissolved organic phosphorous (to PO43-) has been documented, the analogous photoproduction of sulfate from dissolved organic sulfur (DOS) has not yet been reported. Recent high-resolution mass spectrometry studies showed a selective loss of organic sulfur during photodegradation of dissolved organic matter, which was hypothesized to result in the production of sulfate. Here, we provide evidence of ubiquitous production of sulfate, methanesulfonic acid (MSA), and methanesulfinic acid (MSIA) during photodegradation of DOM samples from a wide range of natural terrestrial environments. We show that photochemical production of sulfate is generally more efficient than the production of MSA and MSIA, as well as volatile S-containing compounds such as CS2 and COS. We also identify possible molecular precursors for sulfate and MSA, and we demonstrate that a wide range of relevant classes of DOS compounds (in terms of S oxidation state and molecular structure) can liberate sulfate upon photosensitized degradation. This work suggests that photochemistry may play a more significant role in the aquatic and atmospheric fate of DOS than currently believed.

Marine versus Continental Sources of Iodine and Selenium in Rainfall at Two European High-Altitude Locations.

The essential elements selenium (Se) and iodine (I) are often present in low levels in terrestrial diets, leading to potential deficiencies. Marine I and Se emissions and subsequent atmospheric wet deposition has been suggested to be an important source of I and Se to soils and terrestrial food chains. However, the contribution of recycled moisture of continental origin to I and Se to precipitation has never been analyzed. Here we report concentrations and speciation of I and Se, as well as of bromine (Br), sulfur (S), and DOC-δ13C signatures for weekly collected precipitation samples (in the period of April 2015 to September 2016) at two high altitude sites, i.e., Jungfraujoch (JFJ; Switzerland) and Pic du Midi (PDM; France). Analysis of precipitation chemistry and moisture sources indicate combined marine and continental sources of precipitation and Se, I, Br, and S at both sites. At JFJ, concentrations of I and Se were highest when continental moisture sources were dominant, indicating important terrestrial sources for these elements. Furthermore, correlations between investigated elements and DOC-δ13C, particularly when continental moisture source contributions were high, indicate a link between these elements and the source of dissolved organic matter, especially for I (JFJ and PDM) and Se (JFJ).

Insights into arsenic retention dynamics of Pleistocene aquifer sediments by in situ sorption experiments.

The migration of arsenic (As) enriched groundwater into Pleistocene aquifers as a consequence of extensive groundwater abstraction represents an increasing threat to the precious water resources in Asian delta regions. Pleistocene aquifer sediments are typically rich in FeIII-(hydr)oxides and are capable to adsorb high amounts of As. This results in a pronounced accumulation of As in Pleistocene aquifers, where high As groundwater infiltrates from adjacent Holocene aquifers. However, As retention by Pleistocene aquifers over long-term time scales remains largely unknown. We studied As sorption in situ by placing natural Pleistocene sediments and pure mineral phases directly inside groundwater monitoring wells at a study site near Hanoi (Vietnam). This in situ exposure allows for constant flushing of the samples with unaltered groundwater and the establishment of undisturbed sorption equilibria similar to those in local aquifer sediments, which is not readily attainable in traditional laboratory sorption experiments. The groundwaters in our experimental wells were characterized by different As concentrations (0.01-6.63 µmol/L) and redox states, reaching from suboxic to anoxic conditions (Eh of +159 to -4 mV). Results show that adsorption is the dominant As retention mechanism, independent from the respective groundwater chemistry (i.e. concentrations of dissolved P, HCO3- and Si). Whilst most of the As sorbed within the first week, sorption further increased slowly but consistently by 6-189%, respectively, within six months. Hence, the As sorption behavior of Pleistocene aquifer sediments should be determined over longer periods to avoid an underestimation of the As sorption capacity. Accompanying desorption experiments revealed that about 51% of the sorbed As was remobilized within six months when exposed to low As groundwater. We therefore conclude that a considerable proportion of the As accumulated in the aquifer sediments is prone to remobilization once the As concentrations in migrating groundwater decline. Remobilization of As should be considered in local water management plans to avoid contamination of precious groundwater resources with this As legacy.

Quantification of Element Fluxes in Wastewaters: A Nationwide Survey in Switzerland.

The number and quantities of trace elements used in industry, (high-tech) consumer products, and medicine are rapidly increasing, but the resulting emissions and waste streams are largely unknown. We assessed the concentrations of 69 elements in digested sewage sludge and effluent samples from 64 municipal wastewater treatment plants as well as in major rivers in Switzerland. This data set, representative of an entire industrialized country, presents a reference point for current element concentrations, average per-capita fluxes, loads discharged to surface waters, and economic waste-stream values. The spatial distribution of many individual elements could be attributed either to predominant geogenic or to anthropogenic inputs. Per-capita element fluxes ranged from <10 µg day-1 (e.g., Au, In, and Lu) to >1 mg day-1 (e.g., Zn, Sc, Y, Nb, and Gd) and >1 g day-1 (e.g., for P, Fe, and S). Effluent loads of some elements contributed significantly to riverine budgets (e.g., 24% for Zn, 50% for P, and 83% for Gd), indicating large anthropogenic inputs via the wastewater stream. At various locations, precious metal concentrations in sludge were similar to those in profitable mining ores, with total flux values of up to 6.8 USD per capita per year or 15 USD per metric ton of dry sludge.