Improvement in municipal wastewater treatment alters lake nitrogen to phosphorus ratios in populated regions.

Large-scale and rapid improvement in wastewater treatment is common practice in developing countries, yet this influence on nutrient regimes in receiving waterbodies is rarely examined at broad spatial and temporal scales. Here, we present a study linking decadal nutrient monitoring data in lakes with the corresponding estimates of five major anthropogenic nutrient discharges in their surrounding watersheds over time. Within a continuous monitoring dataset covering the period 2008 to 2017, we find that due to different rates of change in TN and TP concentrations, 24 of 46 lakes, mostly located in China's populated regions, showed increasing TN/TP mass ratios; only 3 lakes showed a decrease. Quantitative relationships between in-lake nutrient concentrations (and their ratios) and anthropogenic nutrient discharges in the surrounding watersheds indicate that increase of lake TN/TP ratios is associated with the rapid improvement in municipal wastewater treatment. Due to the higher removal efficiency of TP compared with TN, TN/TP mass ratios in total municipal wastewater discharge have continued to increase from a median of 10.7 (95% confidence interval, 7.6 to 15.1) in 2008 to 17.7 (95% confidence interval, 13.2 to 27.2) in 2017. Improving municipal wastewater collection and treatment worldwide is an important target within the 17 sustainable development goals set by the United Nations. Given potential ecological impacts on biodiversity and ecosystem function of altered nutrient ratios in wastewater discharge, our results suggest that long-term strategies for domestic wastewater management should not merely focus on total reductions of nutrient discharges but also consider their stoichiometric balance.

Dynamic Modeling and Target Loads of Sulfur and Nitrogen for Surface Waters in Finland, Norway, Sweden, and the United Kingdom.

The target load concept is an extension of the critical load concept of air pollution inputs to ecosystems. The advantage of target loads over critical loads is that one can define the deposition and the point in time (target year) when the critical (chemical) limit is no longer violated. This information on the timing of recovery requires dynamic modeling. Using a well-documented dynamic model, target loads for acidic deposition were determined for 848 surface waters across Finland, Norway, Sweden, and the United Kingdom for the target year 2050. In the majority of sites ( n = 675), the critical ANC-limit was predicted to be achieved by 2050; however, for 127 sites, target loads were determined. In addition, 46 sites were infeasible, i.e., even a reduction of anthropogenic deposition to zero would not achieve the limit by 2050. The average maximum target load for sulfur was 38% lower than the respective critical load across the study lakes ( n = 127). Target loads on a large regional scale can inform effects-based emission reduction policies; the current assessment suggests that reductions beyond the Gothenburg Protocol are required to ensure surface water recovery from acidification by 2050.

Assessing Air-Surface Exchange and Fate of Mercury in a Subtropical Forest Using a Novel Passive Exchange-Meter Device.

A novel passive exchange meter (EM) device was developed to assess air-surface exchange and leaching of Hg in a forest floor. Flux measurements were carried out in a subtropical forest ecosystem during a full year. Over 40% of the Hg fixed in fresh forest litter was remobilized in less than 60 days in warm and humid conditions as a response to rapid turnover of labile organic matter (OM). A two-block experiment including understory and clearing showed that losses of Hg covaried with seasonal conditions and was significantly affected by forest coverage. The process controlling the bulk loss of total Hg from the litter was volatilization, which typically represented 76-96% of the loss processes (Floss). The Floss ranges were 520-1370 and 165-942 ng m-2 d-1 in the understory and clearing, respectively. On a yearly basis, deposition of airborne Hg exceeded total losses by a factor of 2.5 in the clearing and 1.5 in the understory. The vegetation litter in this subtropical forest therefore represented a net sink of atmospheric Hg. This study provided a novel approach to Hg air-soil exchange measurements and further insights on the link between Hg remobilization and OM turnover along with its environmental drivers.

Modelling Environmental Impacts of Cesium-137 Under a Hypothetical Release of Radioactive Waste.

Waste tanks at the nuclear facility located at Sellafield, UK, represent a nuclear source which could release radionuclides to the atmosphere. A model chain which combines atmospheric transport, deposition as well as riverine transport to sea has been developed to predict the riverine activity concentrations of 137Cs. The source term was estimated to be 9 × 104 TBq of 137Cs, or 1% of the assumed total 137Cs inventory of the HAL (Highly Active Liquid) storage tanks. Air dispersion modelling predicted 137Cs deposition reaching 127 kBq m-2 at the Vikedal catchment in Western Norway. Thus, the riverine transport model predicted that the activity concentration of 137Cs in water at the river outlet could reach 9000 Bq m-3 in the aqueous phase and 1000 Bq kg-1 in solid phase at peak level. The lake and river reaches showed different transport patterns due to the buffering effects caused by dilution and slowing down of water velocity.

The organic pollutant status of rivers in Bosnia and Herzegovina as determined by a combination of active and passive sampling methods.

There is an overall lack of data concerning the pollution status of Bosnia Herzegovina, which is confounded by fragmented national environmental management. The present study aimed to provide some initial data for concentrations of priority substances in two major Bosnian Rivers, using two types of passive sampler (PS) as well as by using high volume water sampling (HVWS). Overall, concentrations of most persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) and legacy pesticides, were shown to be low. However, around the town of Doboj on the Bosna River, concentrations of polycyclic aromatic hydrocarbons (PAH) breached European standards for several compounds and reached 67 ng L-1 for freely dissolved concentrations and 250 ng L-1 for total concentrations. In general, contamination was lower in the Neretva River compared to the Bosna, although for brominated diphenyl ethers (PBDEs), results suggested an active source of PBDEs at one location based on the ratio of congeners 47 and 99. Direct comparisons between the different sampling techniques used are not straightforward, but similar patterns of PAH contamination were shown by HVWS and PS in the Bosna River. There are both scientific and practical considerations when choosing which type of sampling technique to apply, and this should be decided based on the goals of each individual study.

Monitoring Effect of SO2 Emission Abatement on Recovery of Acidified Soil and Streamwater in Southwest China.

Following Europe and North America, East Asia has become a global hotspot of acid deposition, with very high deposition of both sulfur (S) and nitrogen (N) occurring in large areas in southwest and southeast China. Great efforts have been made in reducing national emission of sulfur dioxide (SO2) since 2006 in China. However, the total emission of nitrogen oxides (NOx) continued to increase until 2011. To evaluate the effects of SO2 and NOx emission abatement on acid deposition and acidification of soil and water, we monitored the chemical composition of throughfall, soil water, and streamwater from 2001 to 2013 in a small, forested catchment near Chongqing city in Southwestern China. The deposition of S decreased significantly, whereas N deposition increased in the recent years. This clearly showed the effect of SO2 abatement but not of NOx. Overall the rate of acid deposition was reduced. However, there was delay in the recovery of soil and surface water from acidification, probably due to desorption of previously stored sulfate (SO42-) and increase in nitrate (NO3-) leaching from soil. The average acid input by N transformations has greatly exceeded the H+ input directly by atmospheric deposition. The reversal of acidification with an increase in pH of soil water, requires additional abatement of emissions of both SO2 and NOx.

Mercury Flows in China and Global Drivers.

Mercury (Hg) pollution control has become an urgent need at global and national scales. This study, for the first time, comprehensively examines Hg flows in Mainland China and uncovers domestic and external causal drivers of China's Hg emissions/releases. Results show that China's Hg input reaches 2643 t in 2010. China discharges 1368 t of Hg to the environment (to air, 633 t; water, 84 t; and land, 651 t). Embedded Hg transfers across production sectors via waste/byproduct flows reduce Hg releases to land, but lead to secondary Hg emissions to air. Such revelations of embedded Hg transfers adjusts China's comprehensive Hg control that would otherwise only tackle primary emitters. Domestic consumption causes 67% of China's Hg emissions/releases, and external consumption induces the remaining 33%. Besides traditional production-side Hg control measures, demand-side measures and international joint efforts are required to effectively combat Hg pollution. Uncovering embedded and embodied Hg flows within the global economy can assist a paradigm shift necessary to make real progress in global Hg control and the implementation of the Minamata Convention on Mercury.

Material Flow for the Intentional Use of Mercury in China.

Intentional use of mercury (Hg) is an important contributor to the release of Hg into the environment. This study presents the first inventory of material flow for intentional use of Hg in China. The total amount of Hg used in China increased from 803 ± 95 tons in 2005 to its peak level of 1272 ± 110 tons in 2011. Vinyl chloride monomer (VCM) production is the largest user of Hg, accounting for over 60% of the total demand. As regulations on Hg content in products are tightening globally against the background of the Minamata Convention, the total demand will decrease. Medical devices will likely still use a significant amount of Hg and become the second largest user of Hg if no proactive measures are taken. Significant knowledge gaps exist in China for catalyst recycling sector. Although more than half of the Hg used is recycled, this sector has not drawn enough attention. There are also more than 200 tons of Hg that had unknown fates in 2011; very little information exists related to this issue. Among the final environmental fates, landfill is the largest receiver of Hg, followed by air, water, and soil.

Mercury analysis in hair: Comparability and quality assessment within the transnational COPHES/DEMOCOPHES project.

Human biomonitoring (HBM) is an effective tool for assessing actual exposure to chemicals that takes into account all routes of intake. Although hair analysis is considered to be an optimal biomarker for assessing mercury exposure, the lack of harmonization as regards sampling and analytical procedures has often limited the comparison of data at national and international level. The European-funded projects COPHES and DEMOCOPHES developed and tested a harmonized European approach to Human Biomonitoring in response to the European Environment and Health Action Plan. Herein we describe the quality assurance program (QAP) for assessing mercury levels in hair samples from more than 1800 mother-child pairs recruited in 17 European countries. To ensure the comparability of the results, standard operating procedures (SOPs) for sampling and for mercury analysis were drafted and distributed to participating laboratories. Training sessions were organized for field workers and four external quality-assessment exercises (ICI/EQUAS), followed by the corresponding web conferences, were organized between March 2011 and February 2012. ICI/EQUAS used native hair samples at two mercury concentration ranges (0.20-0.71 and 0.80-1.63) per exercise. The results revealed relative standard deviations of 7.87-13.55% and 4.04-11.31% for the low and high mercury concentration ranges, respectively. A total of 16 out of 18 participating laboratories the QAP requirements and were allowed to analyze samples from the DEMOCOPHES pilot study. Web conferences after each ICI/EQUAS revealed this to be a new and effective tool for improving analytical performance and increasing capacity building. The procedure developed and tested in COPHES/DEMOCOPHES would be optimal for application on a global scale as regards implementation of the Minamata Convention on Mercury.

New insights into traditional health risk assessments of mercury exposure: implications of selenium.

There is increasing evidence that selenium (Se) has a significant effect on mercury (Hg) toxicology; however, Hg exposure risk assessments usually consider only the amount of Hg present in the environment or in food. On the basis of the present understanding of mechanisms of interaction between Se and Hg, the physiology/toxicology of Se, and the toxicology of Hg, we propose a new criterion for Se/Hg exposure assessment. This criterion, which is based on Se-Hg interactions, considers not only the toxicological consequences of Hg exposure but also the benefits and/or adverse effects of Se intake, especially the adverse effects related to a Se deficiency/excess. According to an illustrative assessment based on the new criterion and nine existing criteria, large knowledge gaps in the traditional assessments of exposure to Hg and/or Se were found, including those that assessed the interactions between Hg and Se. These results suggest that future assessments of Hg exposure (or Se intake) should include both Se and Hg.

Delayed recovery of surface water chemistry from acidification in subtropical forest region of China.

The three largest acid rain regions of current earth are located in northern and western Europe, eastern North America, and East Asia. Sulfur and nitrate concentrations in headwater streams in Europe and North America decreased as atmospheric sulfur and nitrogen deposition decreased, albeit with a considerable delay. However, how water chemistry responds to the declining sulfur and nitrogen deposition in China is unclear. The regional survey of surface water chemistry during 2010 and 2018 within the Sichuan Basin in southwestern China showed that the recovery of the surface water chemistry was delayed for at least 5 years owing to the release of previously deposited sulfur and nitrogen stored in the soil. After sulfur deposition declined from its peak value, the subregions of purplish soil with low sulfate adsorption capacity still exhibited a net sulfur release in 2010, but this release was no longer evident by 2018. The subregions with the red and yellow soils, which have a high sulfate adsorption capacity, operated as sulfur sinks during 2010 and 2018, indicating a continuous immobilization process through sulfate reduction despite a decrease in sulfur deposition. Additionally, this sulfate reduction countered the release of sulfate caused by sulfur desorption. There was a substantial nitrogen sink within the Sichuan Basin. Nitrogen leaching decreased slowly with the declined nitrogen deposition, except in regions where nitrogen deposition exceeded the critical threshold. Compared to temperate forest regions in Europe, the Sichuan Basin and its surrounding areas have experienced higher decline rates in the leaching of sulfur and nitrogen, highlighting that the subtropical forest region undergoes a faster restoration of surface water chemistry.

A probe into the acid deposition mitigation path in China over the last four decades and beyond.

China currently has the highest acid deposition globally, yet research on its status, impacts, causes and controls is lacking. Here, we compiled data and calculated critical loads regarding acid deposition. The results showed that the abatement measures in China have achieved a sharp decline in the emissions of acidifying pollutants and a continuous recovery of precipitation pH, despite the drastic growth in the economy and energy consumption. However, the risk of ecological acidification and eutrophication showed no significant decrease. With similar emission reductions, the decline in areas at risk of acidification in China (7.0%) lags behind those in Europe (20%) or the USA (15%). This was because, unlike Europe and the USA, China's abatement strategies primarily target air quality improvement rather than mitigating ecological impacts. Given that the area with the risk of eutrophication induced by nitrogen deposition remained at 13% of the country even under the scenario of achieving the dual targets of air quality and carbon dioxide mitigation in 2035, we explored an enhanced ammonia abatement pathway. With a further 27% reduction in ammonia by 2035, China could largely eliminate the impacts of acid deposition. This research serves as a valuable reference for China's future acid deposition control and for other nations facing similar challenges.

First report of a Chinese PFOS alternative overlooked for 30 years: its toxicity, persistence, and presence in the environment.

This is the first report on the environmental occurrence of a chlorinated polyfluorinated ether sulfonate (locally called F-53B, C8ClF16O4SK). It has been widely applied as a mist suppressant by the chrome plating industry in China for decades but has evaded the attention of environmental research and regulation. In this study, F-53B was found in high concentrations (43-78 and 65-112 µg/L for the effluent and influent, respectively) in wastewater from the chrome plating industry in the city of Wenzhou, China. F-53B was not successfully removed by the wastewater treatments in place. Consequently, it was detected in surface water that receives the treated wastewater at similar levels to PFOS (ca. 10-50 ng/L) and the concentration decreased with the increasing distance from the wastewater discharge point along the river. Initial data presented here suggest that F-53B is moderately toxic (Zebrafish LC50-96 h 15.5 mg/L) and is as resistant to degradation as PFOS. While current usage is limited to the chrome plating industry, the increasing demand for PFOS alternatives in other sectors may result in expanded usage. Collectively, the results of this work call for future assessments on the effects of this overlooked contaminant and its presence and fate in the environment.

Screening for Stockholm Convention persistent organic pollutants in the Bosna River (Bosnia and Herzogovina).

The Stockholm Convention, which aspires to manage persistent organic pollutants (POPs) at the international level, was recently ratified in Bosnia and Herzegovina (BiH). Despite this fact, there is in general a paucity of data regarding the levels of POPs in the environment in BiH. In the present study, screening for POPs was conducted in one of the country's major rivers, the Bosna. A two-pronged approach was applied using passive samplers to detect the freely dissolved and bioavailable concentrations in the water phase and sediment analysis to provide an integrated measure of historical contamination. At several places along the river, the concentrations of polycyclic aromatic hydrocarbons (PAH) were high and exhibited potential for both chronic and acute effects to biota. River water also showed elevated concentrations of PAH, up to 480 ng L(-1) near the city of Doboj, and diagnostic ratios suggested combustion sources for the contamination present in both types of sample. The levels of the other contaminants measured-polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers--were generally low in the water phase. However, PCBs and some OCPs were present in river sediments at levels which breach the international criteria and thus suggest potential for ecological damage. Additionally, the levels of heptachlor breached these criteria in many of the sites investigated. This study presents the first screening data for some of these Stockholm Convention relevant compounds in BiH and reveals both low concentrations of some chemical groups, but significant point sources and historic contamination for others.

Selenium in soil inhibits mercury uptake and translocation in rice (Oryza sativa L.).

A great number of studies have confirmed that mercury-selenium (Hg-Se) antagonism is a widespread phenomenon in microorganisms, fish, poultry, humans, and other mammals. However, by comparison, little attention has been paid to plants. To investigate the influence of Se on the uptake and translocation of methylHg/inorganic Hg (MeHg/IHg) in the rice-soil system, we determined the levels of Se, IHg, and MeHg in different parts of rice plants (including the root, stem, leaf, husk, and grain (brown rice)) and corresponding soils of root zones collected from a Hg mined area, where Hg and Se co-occur due to historic Hg mining and retorting activities. The results showed that, in general, the Se levels were inversely related to the levels of both IHg and MeHg in the grains. In addition, a consistent reduction in translocation of both IHg and MeHg in the aerial shoots (i.e., the stem, leaf, husk, and grain) with increasing Se levels in the soils was observed. Furthermore, the Se levels were positively correlated with the IHg levels in the soils and the roots. These results suggest that Se may play an important role in limiting the bioaccessibility, absorption, and translocation/bioaccumulation of both IHg and MeHg in the aerial rice plant, which may be related to the formation of an Hg-Se insoluble complex in the rhizospheres and/or roots.

Decreasing mercury levels in consumer fish over the three decades of increasing mercury emissions in China.

Fish consumption is the primary dietary route of human exposure to methylmercury. It has been well documented that elevated mercury concentration in fish in North America and Europe is linked to anthropogenic mercury emissions. China is the world's largest producer, consumer, and emitter of mercury, as well as the world's largest commercial fish producer and consumer. Although mercury pollution in fish in China is currently receiving much attention worldwide, its status remains largely unknown. Here, we conducted a meta-analysis on total mercury concentrations in marine and freshwater fish samples, covering 35,464 samples collected in China over the past 30 years. It is found that, opposite to the increasing emission and documented mercury contamination events, mercury levels in fish have gradually decreased in China over the past 30 years. The results were in sharp contrast to those found in North America and Europe. The mercury concentrations in fish were significantly anticorrelated with the fish catch and fish aquaculture and were inverse to trophic levels. Overfishing and the short lifecycle of aquaculture fish, both reducing the trophic level and the duration of mercury accumulation, were the most likely causes leading to the decline of mercury concentrations found in fish in China.

Critical loads of headwater streams in China using SSWC model modified by comprehensive F-factor.

In order to evaluate the potential risk of surface water acidification in regions with historically-elevated acid deposition and to measure the recovery of such ecosystems after policy changes, critical loads and their exceedances were estimated for 349 headwater streams across China using a modified SSWC model. Such a model considered the acid-neutralizing capacity derived from high base cation deposition and the robust retention of sulfate and nitrate. Results indicated that China's streams had higher critical loads (averaged at 4.7 keq·ha-1·yr-1) and were less sensitive to acid deposition as compared to Europe and North America. The proportion of surveyed streams with acid deposition exceeded critical load decreased from 40.4% in 2005 to 29.5% in 2018, indicating a significant decrease in risk of surface water acidification, and thus a benefit from the emission abatement in recent years. Nonetheless, a relatively high risk of acidification still existed in southeast China with lower critical loads and most critical load exceedances. More efforts should be put into implementing emission control policies in the future.

Deposition and leaching of sulfur, nitrogen and calcium in four forested catchments in China: implications for acidification.

Here we present the first detailed study on fluxes of sulfur (S), nitrogen (N), and major cations in Chinese subtropical forest catchments. Data are from four study sites, differing in inputs of atmospheric pollutants and sensitivity to acidification. Results show important differences from most sites in North America and Europe. Dry deposition of S, N, and calcium (Ca) is considerably larger than wet deposition in most cases causing deposition fluxes ranging from moderate to very high, both for acidifying compounds (S deposition 1.5-10.5 kiloequivalents per hectare and year (keq ha(-1) yr(-1)); N deposition 0.4 to 2.5 keq ha(-1) yr(-1)) and for alkaline compounds (Ca deposition 0.8 to 5.7 keq ha(-1) yr(-1)). More than half of the input of acidity is neutralized by alkalinity associated with Ca deposition. Furthermore, the retention of incoming S and N is small in the soil root zone, but considerable in the deeper soils or riparian zone. Drainage water from the root zone of the soils at the two sites with the highest deposition show pronounced acidification. For the two sites with moderate deposition inputs, the root zones are retaining some of the incoming S and buffer some of the incoming acidity. The subsoils and the riparian zonesare strong sinks for N, S, and Ca. This is associated with substantial acid neutralization at all sites. These features are of major importance for the understanding of the long-term effects of acidification in China.