Risk characterization, assessment, and management of organic pollutants in beneficially used residual products

A wide array of organic chemicals occur in biosolids and other residuals recycled to land. The extent of our knowledge about the chemicals and the impact on recycling programs varies from high to very low. Two significant challenges in regulating these materials are to accurately determine the concentrations of the organic compounds in residuals and to appropriately estimate the risk that the chemicals present from land application or public distribution. This paper examines both challenges and offers strategies for assessing the risks related to the occurrence of organic compounds in residuals used as soil amendments. Important attributes that must be understood to appropriately characterize and manage the potential risks for organic chemicals in biosolids include toxicity and dose response, transport potential, chemical structure and environmental stability, analytical capability in the matrix of interest, concentrations and persistence in waste streams, plant uptake, availability from surface application versus incorporation, solubility factors, and environmental fate. This information is complete for only a few chemicals. Questions persist about the far greater number of chemicals for which toxicity and environmental behavior are less well understood. This paper provides a synopsis of analytical issues, risk assessment methodologies, and risk management screening alternatives for organic constituents in biosolids. Examples from experience in Wisconsin are emphasized but can be extrapolated for broader application.     

Beneficial reuse and sustainability: the fate of organic compounds in land-applied waste

Land application systems, also referred to as beneficial reuse systems, are engineered systems that have defined and permitted application areas based on site and waste characteristics to determine the land area size requirement. These terrestrial systems have orders of magnitude greater microbial capability and residence time to achieve decomposition and assimilation compared with aquatic systems. In this paper we focus on current information and information needs related to terrestrial fate pathways in land treatment systems. Attention is given to conventional organic chemicals as well as new estrogenic and pharmaceutical chemicals of commerce. Specific terrestrial fate pathways addressed include: decomposition, bound residue formation, leaching, runoff, and crop uptake. Molecular decomposition and formation of bound residues provide the basis for the design and regulation of land treatment systems. These mechanisms allow for assimilation of wastes and nondegradation of the environment and accomplish the goal of sustainable land use. Bound residues that are biologically produced are relatively immobile, degrade at rates similar to natural soil materials, and should present a significantly reduced risk to the environment as opposed to parent contaminants. With regard to leaching and runoff pathways, no comprehensive summary or mathematical model of organic chemical migration from land treatment systems has been developed. For the crop uptake pathway, a critical need exists to develop information for nonagricultural chemicals and to address full-scale performance and monitoring at more land application sites. The limited technology choices for treatment of biosolids, liquids, and other wastes implies that acceptance of some risks and occurrence of some benefits will continue to characterize land application practices that contribute directly to the goal of beneficial reuse and sustainability.     

Photodegradation of the endocrine-disrupting chemical 4-nonylphenol in biosolids applied to soil

There is increasing concern about the environmental fate and impact of biosolids-associated anthropogenic organic chemicals, among which 4-nonylphenol (4-NP) is one of the most studied chemicals. This is primarily because 4-NP is an endocrine disruptor and has been frequently detected in environmental samples. Due to its high hydrophobicity, 4-NP has high affinity for biosolids. Land application of 4-NP-containing biosolids could potentially introduce large quantities of this chemical into the environment. A laboratory experiment was conducted to investigate the effect of artificial sunlight on 4-NP degradation in biosolids applied to soil. When exposed to artificial sunlight for 30 d, the top-5-mm layer of biosolids showed a 55% reduction of 4-NP, while less than 15% of the 4-NP was degraded when the biosolids were kept in the dark. Our results indicate that sensitized photolysis reaction plays an important role in reducing the levels of 4-NP in land-applied biosolids. Surface application rather than soil incorporation of biosolids could be effective in reducing biosolids-associated organic chemicals that can be degraded through photolysis reactions. However, the risks of animal ingestion, foliar deposition, and runoff should also be evaluated when biosolids are applied on the soil surface.     

Estimated occupational risk from bioaerosols generated during land application of class B biosolids

Some speculate that bioaerosols from land application of biosolids pose occupational risks, but few studies have assessed aerosolization of microorganisms from biosolids or estimated occupational risks of infection. This study investigated levels of microorganisms in air immediately downwind of land application operations and estimated occupational risks from aerosolized microorganisms. In all, more than 300 air samples were collected downwind of biosolids application sites at various locations within the United States. Coliform bacteria, coliphages, and heterotrophic plate count (HPC) bacteria were enumerated from air and biosolids at each site. Concentrations of coliforms relative to Salmonella and concentrations of coliphage relative to enteroviruses in biosolids were used, in conjunction with levels of coliforms and coliphages measured in air during this study, to estimate exposure to Salmonella and enteroviruses in air. The HPC bacteria were ubiquitous in air near land application sites whether or not biosolids were being applied, and concentrations were positively correlated to windspeed. Coliform bacteria were detected only when biosolids were being applied to land or loaded into land applicators. Coliphages were detected in few air samples, and only when biosolids were being loaded into land applicators. In general, environmental parameters had little impact on concentrations of microorganisms in air immediately downwind of land application. The method of land application was most correlated to aerosolization. From this large body of data, the occupational risk of infection from bioaerosols was estimated to be 0.78 to 2.1%/yr. Extraordinary exposure scenarios carried an estimated annual risk of infection of up to 34%, with viruses posing the greatest threat. Risks from aerosolized microorganisms at biosolids land application sites appear to be lower than those at wastewater treatment plants, based on previously reported literature.     

Biosolids-derived nitrogen mineralization and transformation in forest soils

Utilization of biosolids through land application is becoming increasingly popular among wastewater managers. To minimize the potential contamination of receiving waters from biosolids-derived nitrogen (N), it is important to understand the availability of N after land application of biosolids. In this study, four secondary biosolids (two municipal and two pulp and paper industrial biosolids) were used in a laboratory incubation experiment to simulate N mineralization and transformation after land application. Municipal biosolids were from either aerobically or anaerobically digested sources, while pulp and paper industrial biosolids were from aerated wastewater stabilization lagoons. These biosolids were mixed with two New Zealand forest soils (top 100 mm of a volcanic soil and a brown soil) and incubated at two temperatures (10 and 20 degrees C) for 26 wk. During incubation, mineralized N was periodically leached from the soil-biosolids mixture with 0.01 M CaCl2 solution and concentrations of NH4 and NO3 in leachate were determined. Mineralization of N from aerobically digested municipal biosolids (32.1%) was significantly more than that from anaerobically digested biosolids (15.2%). Among the two pulp and paper industrial biosolids, little N leached from one, while as much as 18.0% of total organic N was leached from the other. As expected, mineralization of N was significantly greater at 20 degrees C (average 22.8%) than at 10 degrees C (average 9.7%). It was observed that more N in municipal biosolids was mineralized in the brown soil, whereas more N in pulp and paper industrial biosolids mineralized in the volcanic soil. Transformation of NH4 to NO3 was affected by soil type and temperature.     

A modified risk assessment to establish molybdenum standards for land application of biosolids

The USEPA standards (40 CFR Part 503) for the use or disposal of sewage sludge (biosolids) derived risk-based numerical values for Mo for the biosolids --> land --> plant --> animal pathway (Pathway 6). Following legal challenge, most Mo numerical standards were withdrawn, pending additional field-generated data using modern biosolids (Mo concentrations <75 mg kg(-1) and a reassessment of this pathway. This paper presents a reevaluation of biosolids Mo data, refinement of the risk assessment algorithms, and a reassessment of Mo-induced hypocuprosis from land application of biosolids. Forage Mo uptake coefficients (UC) are derived from field studies, many of which used modern biosolids applied to numerous soil types, with varying soil pH values, and supporting various crops. Typical cattle diet scenarios are used to calculate a diet-weighted UC value that realistically represents forage Mo exposure to cattle. Recent biosolids use data are employed to estimate the fraction of animal forage (FC) likely to be affected by biosolids applications nationally. Field data are used to estimate long-term Mo leaching and a leaching correction factor (LC) is used to adjust cumulative biosolids application limits. The modified UC and new FC and LC factors are used in a new algorithm to calculate biosolids Mo Pathway 6 risk. The resulting numerical standards for Mo are cumulative limit (RPc)=40 kg Mo ha(-1), and alternate pollutant limit (APL) = 40 mg Mo kg(-1) We regard the modifications to algorithms and parameters and calculations as conservative, and believe that the risk of Mo-induced hypocuprosis from biosolids Mo is small. Providing adequate Cu mineral supplements, standard procedure in proper herd management, would augment the conservatism of the new risk assessment.     

当前化学品环境管理的挑战与建议

化学品环境管理是我国当前环境保护工作中亟需加强的重要领域,并且面临三大挑战:化学品种类呈爆发式增长,化学品的生产使用量呈指数式增长以及对化学品的损害特性认知滞后。现阶段,我国的化学品管理集中在对生产流通环节的安全事故防范和对次生环境污染的治理与应对,但是对化学品造成的环境影响和健康损害却还缺乏足够的重视,相应的风险管控制度和防治体系建设也还处于摸索阶段。本文从管理对象界定、化工行业管理、管理制度设计、专业能力建设和多学科技术支撑五个方面梳理了我国当前化学品环境管理工作中存在的主要问题和不足。综合我国化学工业的发展现状和化学品环境管理的现实需求,建议从五个方面加强化学品环境管理体系的建设:(1)明确化学品环境管理的对象和范围,科学制定管理战略与路线;(2)深化对化工行业发展规律的认知,加快形成行业绿色转型的共识与行动;(3)定期跟踪评估政策的实施成效,建立完善的政策调整机制;(4)总结和借鉴国内外化学品环境管理的先进经验和教训;(5)加强化学品全流程、跨领域的研究整合,大力发展检测、模拟和评估的新技术与新方法。本研究可为我国中长期化学品环境管理战略和政策制度体系的建立提供决策支持。     

Phosphorus release from a biosolids-amended sandy spodosol

Most regulations governing biosolids land application do not consider that phosphorus (P) solubility can vary widely among biosolids. Current regulations typically group all biosolids together in one category or group biosolids together with manures. Research has shown that not all biosolids have the same potential to affect the environment when land applied, but the database is limited. The purpose of this study was to characterize P release from several biosolids produced and/or marketed in Florida. A small soil column dynamic laboratory incubation was conducted to assess P release potential. Eleven biosolids and a mineral fertilizer (triple super phosphate) were individually mixed with a typical low-P sorbing Florida soil (Immokalee fine sand) at 56 and 224 kg P ha(-1). Columns were periodically leached over 5.5 mo to attain 60 mL (1/2 pore volume) of drainage in each leaching. Soluble reactive P was determined and summed over the eight leachings to represent total P source release. Cumulative P release (as a percentage of P applied) was greatest from biological P removal (BPR) and BPR-like biosolids and least from heat-dried materials. Phosphorus release from biosolids depends on biosolids treatment type (digestion) and P chemistry, suggesting that biosolids regulations must account for differences in P lability to accurately gauge environmental risk.     

Phosphorus restrictions for land application of biosolids: current status and future trends

The application of biosolids (sewage sludge) to agricultural soils provides P in excess of crop needs when applied to meet the N needs of most agronomic crops. These overapplications can result in the buildup of P in soils to values well above those needed for optimum crop yields and also may increase risk of P losses to surface and ground waters. Because of concerns regarding the influence of P on water quality in the USA, many state and federal agencies now recommend or require P-based nutrient management plans for animal manures. Similar actions are now under consideration for the land application of biosolids. We reviewed the literature on this subject and conducted a national survey to determine if states had restrictions on P levels in biosolids-amended soils. The literature review indicates that while the current N-based approach to biosolids management does result in increases of soil P, some properties of biosolids may mitigate the environmental risk to water quality associated with land application of P in biosolids. Results of the survey showed that 24 states have regulations or guidelines that can be imposed to restrict land application of biosolids based on P. Many of these states use numerical thresholds for P in biosolids-amended soils that are based on soil test phosphorus (STP) values that are much greater than the values considered to be agronomically beneficial. We suggest there is the need for a comprehensive environmental risk assessment of biosolids P. If risk assessment suggests the need for regulation of biosolids application, we suggest regulations be based on the P Site Index (PSI), which is the method being used by most states for animal manure management.     

Characterization of phosphorus species in biosolids and manures using XANES spectroscopy

Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(2) = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.     

Determination of phosphorus source coefficients for organic phosphorus sources: laboratory studies

Phosphorus losses in runoff from application of manures and biosolids to agricultural land are implicated in the degradation of water quality in the Chesapeake and Delaware Inland Bays. We conducted an incubation study to determine the relative P solubility and bioavailability, referred to as P source coefficients (PSCs), for organic P sources, which are typically land-applied in the Mid-Atlantic USA. Nine organic and one inorganic (KH2PO4) P amendments were applied to an Evesboro loamy sand (mesic, coated Typic Quartzipsamments) at a rate of 60 mg P kg(-1) and incubated for 8 wk with subsamples analyzed at 2 and 8 wk. There was an increase in Mehlich-3 P (M3-P), water-soluble P (WS-P), iron-oxide strip extractable P (FeO-P), and Mehlich-3 P saturation ratio (M3-PSR) with P additions, which varied by P source. The trend of relative extractable WS-P, FeO-P, and M3-P generally followed the pattern: inorganic P > liquid and deep pit manures > manures and biosolids treated with metal salts or composted. We found significant differences in the availability of P from varying organic P sources. The use of PSCs may be beneficial when determining the risk of P losses from land application of manures and other organic P sources and could be used in risk assessments such as a P site index. These PSCs may also be useful for determining P application rates when organic P sources are applied to P deficient soils for use as a fertilizer source.     

Risk perception, risk communication, and stakeholder involvement for biosolids management and research

An individual's perception of risk develops from his or her values, beliefs, and experiences. Social scientists have identified factors that affect perceptions of risk, such as whether the risk is knowable (uncertainty), voluntary (can the individual control exposure?), and equitable (how fairly is the risk distributed?). There are measurable differences in how technical experts and citizen stakeholders define and assess risk. Citizen knowledge and technical expertise are both relevant to assessing risk; thus, the 2002 National Research Council panel on biosolids recommended stakeholder involvement in biosolids risk assessments. A survey in 2002 identified some of the factors that influence an individual's perception of the risks involved in a neighbor's use of biosolids. Risk communication was developed to address the gap between experts and the public in knowledge of technical topics. Biosolids management and research may benefit from applications of current risk communication theory that emphasizes (i) two-way communications (dialogue); (ii) that the public has useful knowledge and concerns that need to be acknowledged; and (iii) that what may matter most is the credibility of the purveyor of information and the levels of trustworthiness, fairness, and respect that he or she (or the organization) demonstrates, which can require cultural change. Initial experiences in applying the dialogue and cultural change stages of risk communication theory--as well as consensus-building and joint fact-finding--to biosolids research suggest that future research outcomes can be made more useful to decision-makers and more credible to the broader public. Sharing control of the research process with diverse stakeholders can make research more focused, relevant, and widely understood.     

Odorants and malodors associated with land application of biosolids stabilized with lime and coal fly ash

Malodor emissions limit public acceptance of using municipal biosolids as natural organic resources in agricultural production. We aimed to identify major odorants and to evaluate odor concentrations associated with land application of anaerobically digested sewage sludges (Class B) and their alkaline (lime and coal fly ash)-stabilized products (Class A). These two types of biosolids were applied at 12.6 tonnes ha(-1) (dry weight) to microplots of very fine clayey Vertisol in the Jezreel Valley, northern Israel. The volatile organic compounds (VOCs) emitted from the biosolids before and during alkaline stabilization and after incorporation into the soil were analyzed by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Odor concentrations at the plots were evaluated on site with a Nasal Ranger field olfactometer that sniffed over a defined land surface area through a static chamber. The odors emitted by anaerobically digested sewage sludges from three activated sludge water treatment plants had one characteristic chemical fingerprint. Alkaline stabilization emitted substantial odors associated with high concentrations of ammonia and release of nitrogen-containing VOCs and did not effectively reduce the potential odor annoyance. Odorous VOCs could be generated within the soil after biosolids incorporation, presumably because of anaerobic conditions within soil-biosolids aggregates. We propose that dimethyl disulfide and dimethyl trisulfide, which seem to be most related to the odor concentrations of biosolids-treated soil, be used as potential chemical markers for the odor annoyance associated with incorporation of anaerobically digested sewage sludges.     

Using data mining to predict soil quality after application of biosolids in agriculture

The amount of biosolids recycled in agriculture has steadily increased during the last decades. However, few models are available to predict the accompanying risks, mainly due to the presence of trace element and organic contaminants, and benefits for soil fertility of their application. This paper deals with using data mining to assess the benefits and risks of biosolids application in agriculture. The analyzed data come from a 10-yr field experiment in northeast France focusing on the effects of biosolid application and mineral fertilization on soil fertility and contamination. Biosolids were applied at agriculturally recommended rates. Biosolids had a significant effect on soil fertility, causing in particular a persistent increase in plant-available phosphorus (P) relative to plots receiving mineral fertilizer. However, soil fertility at seeding and crop management method had greater effects than biosolid application on soil fertility at harvest, especially soil nitrogen (N) content. Levels of trace elements and organic contaminants in soils remained below legal threshold values. Levels of extractable metals correlated more strongly than total metal levels with other factors. Levels of organic contaminants, particularly polycyclic aromatic hydrocarbons, were linked to total metal levels in biosolids and treated soil. This study confirmed that biosolid application at rates recommended for agriculture is a safe option for increasing soil fertility. However, the quality of the biosolids selected has to be taken into account. The results also indicate the power of data mining in examining links between parameters in complex data sets.     

Risk management is part of good management

As the use of hazard and risk assessments becomes more commonplace, the need for and importance of an overall risk management system become apparent. Such a system allows companies to prioritize both their efforts to identify and understand risks and their allocation of resources to manage and control risks. In the future, the most effective risk management systems will be integrated into other business processes and management systems, to ensure that their value as well as their costs are recognized and measured by line operations. For example, chemical and petrochemical companies such as BP Exploration, Monsanto, and Union Carbide are improving on well-established risk management systems by increasing their businesses' involvement in and ownership of the process. This article summarizes the key elements of a risk management system and uses the lessons learned by various companies to define best existing and emerging practices.     

Occurrence and fate of pharmaceuticals and personal care products (PPCPs) in biosolids

Each year, large quantities of pharmaceuticals and personal care products (PPCPs) are used worldwide. Once conveyed to wastewater treatment plants, PPCPs can remain unchanged or undergo partial or complete transformation during wastewater treatment processes before discharge into the environment via effluent and biosolids for land application. Biosolids can be a major sink for some PPCPs. Previous investigations have indicated that land application of biosolids may be a potential important route through which PPCPs enter the environment. However, no information is available on exactly how closely the concentrations of PPCPs in the environmental media are related to the land application of PPCP-containing biosolids. This paper reviews currently available information on the occurrence of PPCPs in biosolids, methods of analysis, the potential fate of PPCPs in biosolids-applied soils, and composting as a potential means for removal of PPCPs from biosolids.     

Nutrient and trace element leaching following mine reclamation with biosolids

Mine reclamation with biosolids increases revegetation success but nutrient addition well in excess of vegetation requirements has the potential to increase leaching of NO3 and other biosolids constituents. A 3-yr water quality monitoring study was conducted on a Pennsylvania mine site reclaimed with biosolids applied at the maximum permitted and standard loading rate of 134 Mg ha(-1). Zero-tension lysimeters were installed at 1-m depth 1 yr before reclamation: three in the biosolids application area, one in a control area (no biosolids). Before reclamation, all water samples had pH in the range 4.7 to 6.2, acidity < 20 mg L(-1), and very low levels of all other measured parameters. Following reclamation, percolate water in the biosolids-treated area had lower pH and greater acidity than the control area. Acidity was greatest during the first winter following biosolids application, decreased during the spring, and showed a similar pattern but with much smaller concentrations the second year. Maximum first- year leachate NO3 concentrations were approximately 300 mg L(-1) and half as large the second year. Estimated inorganic N leaching loss during the first 2 yr after biosolids application was 2327 kg N ha(-1). Aluminum, Mn, Cu, Ni, Pb, and Zn followed similar leaching patterns as did acidity, and their mobilization appeared to be the result of the increased acidity. These results indicate that large applications of low-C/N-ratio biosolids could negatively impact area water quality and that biosolids reclamation practices should be modified to reduce this possibility.     

Chemical fractionation of phosphorus in stabilized biosolids

Three chemicals-ferrous sulfate (FeSul), calcium oxide (CaO), and aluminum sulfate (alum)-were applied at different rates to stabilize P in fresh, anaerobically digested biosolids (FBS) obtained from an activated sewage treatment plant. A modified Hedley fractionation procedure was used to assess P forms in these sludge-borne materials and in a biosolids compost (BSC) prepared from the same FBS. Each biosolids material exhibited a unique pattern of P distribution among fractions. The most available P forms, namely: (i) water-soluble P (WSP); (ii) membrane-P; and (iii) NaHCO(3)-P, were stabilized by small rates of each of the chemicals; but the P transformation into more stable forms depended on the type of chemical added. The stabilized P forms were enhanced by high rates of CaO and FeSul, but were reduced by high rates of alum. The organic P (P(o)) in the first three fractions of the FeSul- and alum-stabilized biosolids was enhanced by the chemical addition, and P(o) transformation from NaOH-P(o) into NaHCO(3)-P(o) was found in calcium-stabilized biosolids. A positive relationship was found between NaHCO(3)-P(o) and the NaHCO(3)-extracted organic C in all chemically stabilized biosolids. One-step extraction by NaHCO(3) or NaOH underestimated P extraction compared to the stepwise extraction. The reported results are consistent with solid-state P speciation reported earlier and contribute important information for optimizing biosolids stabilization to reduce P loss after incorporation in soils and for maximizing soil capacity to safely store pre-stabilized biosolids.     

Relative cancer risks of chemical contaminants in the great lakes

Anyone who drinks water or eats fish from the Great Lakes consumes potentially carcinogenic chemicals. In choosing how to respond to such pollution, it is important to put the risks these contaminants pose in perspective. Based on recent measurements of carcinogens in Great Lakes fish and water, calculations of lifetime risks of cancer indicate that consumers of sport fish face cancer risks from Great Lakes contaminants that are several orders of magnitude higher than the risks posed by drinking Great Lakes water. But drinking urban groundwater and breathing urban air may be as hazardous as frequent consumption of sport fish from the Great Lakes. Making such comparisons is difficult because of variation in types and quality of information available and in the methods for estimating risk. Much uncertainty pervades the risk assessment process in such areas as estimating carcinogenic potency and human exposure to contaminants. If risk assessment is to be made more useful, it is important to quantify this uncertainty.