The approach proposed was to identify the relative potential of different types of WEEE in producing adverse human health effects when undergoing open burning. To address this, data on the material composition of different end-of-life electronic items (mobile PCBs, computer PCBs, and wires) were obtained from scientific and technical literature studies.
Although limited in number, the information dealing with the concentration of both metals and plastic components for these items was subjected to an appropriate level of peer review/quality assurance (Cesaro et al. 2018), to provide the most reliable data set for the analysis.
WEEE composition
Printed circuit boards from personal computers and mobile phones
The PCB is an ingenious design solution, which has enabled a very dense array of electronic components (e.g., switches, capacitors, diodes, etc.) to function in a highly limited space. PCBs provide mechanical support for the electronic components and secure their electrical connection using conductive etched tracks. Based on the number of layers of the conductive tracks, PCBs can be subdivided into three major groups: single-, double-, and multi-layered. With the addition of further conductive layers, it is possible to populate the PCBs more densely with electronic components (Yamane et al. 2011). However, for practical reasons in the recycling industry, the classification of PCBs is based on devices or group of devices from which the PCBs originate, e.g., from personal computers (PCs), from mobile phones, and from small household appliances.
Along with this universal application in technology, PCBs have also highly complex material composition. A single PCB can contain more than 40 different materials (Lu and Xu 2016). Materials contained in the PCBs can be generally divided into three groups: metals, plastics, and non-metallic inorganic substances. The plastics and inorganic plastic substances are generally identified in the scientific literature as a non-metal fraction (NMF) and make between 60–70 wt% of the PCBs. Metal contained in the PCBs ranges between 30–40 wt% of the PCBs (Zheng et al. 2009; Veit et al. 2014). However, unlike NMF fraction, which remains consistent across various types of PCBs, the metal content is highly dependent on the function of the device. For example, the mass share of the total metal fraction and the concentration of the most valuable metals, i.e., Cu and Au, is significantly higher in the PCBs originating from mobile phones than in those from PCs.
There are several types of PCB substrate currently in use, but approx. 70% of all types of PCBs have a FR-4 type of substrate. The FR-4 substrates, as classified by the National Electrical Manufacturers Association (NEMA), are made of multiple layers of laminate made of epoxy-reinforced resins. Furthermore, the FR-4 substrate is used where flame retardants are required. In general, the NMF of PCB consists of 65 wt% of glass fibers, 32 wt% epoxy resin, and < 3 wt% of impurities (Kumar et al. 2018).
Based on their economic value and their relative concentrations, the metals contained in PCB can be segregated into base metals, trace, and precious metals. The base metals mainly include Cu, Fe, Al, Pb, Sn, Zn, and Ni with concentration range between 25–30 wt% (Cu) down to 0.5–1 wt% (Ni or Zn). The trace and precious metals are present in concentrations between 1 and 20,000 ppm. The concentrations and the presence of trace and precious metals are significantly more volatile than that of base metals (Işıldar et al. 2016; Kaya 2016; Evangelopoulos et al. 2017).
Data on the material composition of PCBs from PCs and mobile phones are summarized in Tables 1 and 2, respectively.
Table 1 Selected elemental composition of PCBs from PCs Table 2 Elemental composition of PCBs from mobile phones Cables and wiring
Rapid development and accessibility of the electrical and electronic equipment (EEE) are associated with the increased production of cables and wires. However, the recycling of cables and wires, due to their varying size and diverse applications, is particularly challenging. The structure of cables and wires is independent of their function: a conductive metal core for transmission of electricity and data usually made of high purity copper, an insulating layer, and a flame-retardant containing protection layer (Suresh et al. 2017). An overview of material composition of several types of cables is provided in Table 3.
Table 3 An overview of material composition of several types of Cu-core cables (Hischier et al. 2007) The shrinking Core model (SCM)
For the purposes of the relative risk assessment, the concentration of metals emitted from the open burning of WEEE was estimated by applying the shrinking core model (SCM). The data dealing with the concentration of metals in air, as reported in scientific literature, are not specifically associated with the open burning practices but a general reference to informal recycling of WEEE. The proportion of different categories of WEEE destined to this practice is not provided, so that linking the metal concentration in air to a fully characterized WEEE category is not possible. Thermodynamic simulations have also been performed (Dong et al. 2015; Yu et al. 2016), but the experimental conditions adopted do not reflect the uncontrolled situation of open burning.
The SCM is widely used to describe fluid–solid reactions that result in the shrinkage of the solid particles. It can apply to different areas, including pharmacokinetics, extractive metallurgy, control of gaseous pollutants, and catalyst regeneration (Gbor and Jia 2004; Fogler 2016). Further applications dealt with adsorption reactions: Fan et al. (2001) used the SCM to describe the behavior of a fixed-bed reactor during the reaction between gas phase H2S and perovskite-type sorbents: Jena et al. (2003) developed a SCM-based mass transfer formulation for batch adsorption processes. In the field of combustion reactions, the SCM is the standard theoretical framework (Sadhukhan et al. 2010; Buckmaster and Jackson 2013; Zhao et al. 2015, 2018; Wang et al. 2016) and it was used, in this work, to model the chemical reaction occurring during the open burning of WEEE.
This can be regarded as a heterogeneous reaction in which a gas, namely the ambient air, surrounds a solid particle and reacts with it. Such reactions are generally represented as follows:
$$ a{A}_{(s)}+b{B}_{(g)}\to c{C}_{(s)}+d{D}_{(g)} $$
(1)
The heterogeneous reactions of solid particles surrounded by a gaseous film can be described by the SCM, assuming that the reaction occurs first at the outer skin of the particle. The reaction zone then moves into the solid, leaving behind completely converted material and inert solid, referred to as ash, so that at any time, there exists an unreacted core of material which shrinks in size during the reaction (Levenspiel 1999). In accordance with the SCM, the reaction can be regarded as the succession of five steps (Levenspiel 1999):
-
1.
Diffusion of the gaseous reactant through the film surrounding the particle to its solid surface;
-
2.
Penetration and diffusion of the gas through the blanket of ash to the surface of the unreacted core;
-
3.
Reaction of the gas with the solid;
-
4.
Diffusion of the gaseous products through the ash back to the exterior surface of the solid;
-
5.
Diffusion of the gaseous products through the gas film back into the main body of the fluid.
For the purposes of this work, the second step can be considered the rate-controlling one. In a gas/solid system such as for combustion, the shrinkage of the unreacted core is indeed much slower than the flow rate of the gas diffusing towards the unreacted core, so that it is possible to consider the shrinking process as being stationary. In this hypothesis, the gas flow within the ash layer can be expressed by the Fick’s law, according to the following expression:
$$ -\frac{1}{S_{\mathrm{ex}}}\frac{\mathrm{dN}}{\mathrm{dt}}=\mathcal{D}\frac{\mathrm{dC}}{\mathrm{dr}}=\mathrm{costant} $$
(2)
where
-
S
ex
:
-
is the unchanging exterior surface of the solid particle;
-
N
:
-
is the number of moles of the gaseous reactant;
-
D
e
:
-
is the effective diffusion coefficient of the gaseous reactant in the ash layer, evaluated considering the porosity and the tortuosity of the solid material;
-
C
:
-
is the concentration of gaseous reactant computed at standard conditions (298.15 K and 101 kPa).
Therefore, assuming that the solid particles involved in the reaction have a spherical shape, the conversion process develops as described by Eq. (2), meaning that the rate of reaction at any instant is given by its rate of diffusion to the reaction surface.
Considering that the mass (m) of a spherical particle is related to the density of its composing material (ρ) by the following expression:
$$ m=\frac{4}{3}\pi {r}^3\rho $$
(3)
Equation (1) can be also written as follows:
$$ \left(-\frac{dN}{dt}\right)\ast \frac{dm}{m^{\frac{4}{3}}}={\mathcal{D}}_{\mathrm{e}}\ast 16{\pi}^2\rho {\left(\frac{3}{4\pi \rho}\right)}^{\frac{4}{3}}\ast \mathrm{dc} $$
(4)
The solution to this equation is given by the following expression:
$$ \left(-\frac{dN}{dt}\right)\ast \left(\frac{1}{m^{\frac{1}{3}}}-\frac{1}{M^{\frac{1}{3}}}\right)={\mathcal{D}}_{\mathrm{e}}\ast \frac{16}{3}{\pi}^2\rho {\left(\frac{3}{4\pi \rho}\right)}^{\frac{4}{3}}\ast {c}_{ag} $$
(5)
where
-
m
:
-
is the mass of the solid particle;
-
M
:
-
is the initial mass of the solid particle;
-
c
ag
:
-
is the bulk concentration of gaseous reactant evaluated.
In order to describe the heterogeneous reaction more realistically, it should be considered that as the solid particle core shrinks, the ash layer becomes thicker, slowing the rate of diffusion of the gas. According to the stoichiometry of a generic chemical reaction:
$$ \left(-\mathrm{d}{\mathrm{N}}_a\right)=\frac{a}{b}\left(-\mathrm{d}{\mathrm{N}}_b\right)=-\frac{a}{b}\frac{\mathrm{dm}}{\mathrm{MW}} $$
(6)
where
- a and b:
-
are the stoichiometric coefficients of the reactants;
-
M
W
:
-
is the molecular weight of the solid reactant.
Considering this equivalence, Eq. (5) is solved using the following expression:
$$ {M}^{\frac{2}{3}}\left\{\left[\left(1-\left(\frac{m}{M}\right)\right)\right]-1,5\bullet \left[1-{\left(\frac{m}{M}\right)}^{\frac{2}{3}}\right]\right\}=-7.795\ast \frac{\mathrm{Mw}\ast b\ast {\mathcal{D}}_{\mathrm{e}}\ast {c}_{\mathrm{ag}}}{a\ast {\rho}^{\frac{1}{3}}}\ast t $$
(7)
In order to reduce the complexity of the mathematical model, an operating temperature of 550°C (823.15 K) was chosen based on previous studies (Gullett et al. 2007; Zhang et al. 2015), and the mass (mg) of ash produced after 1 h combustion of 1 t of WEEE components was obtained for the selected metals, to allow an estimate of the corresponding concentration in air (shown in Table 4).
Table 4 Mass of metallic ash and corresponding air concentrations from 1-h open burning of WEEE The relative risk assessment
It was possible to estimate the concentration of metals released from the open burning of different types of WEEE, assuming a working time of 10 h.
For organic pollutants, the emitted concentrations in air were estimated on the basis of estimates previously reported in scientific literature (Gullett et al. 2007; Moltó et al. 2011; Zhang et al. 2015).
The emitted concentration of the i-th contaminant was used to estimate the exposure concentration (ECI), as described in the following equation:
$$ {\mathrm{EC}}_{\mathrm{I}}=\frac{C_{\mathrm{i}}\bullet \mathrm{ET}\bullet \mathrm{EF}\bullet \mathrm{ED}}{\mathrm{AT}} $$
(8)
where
-
C
I
:
-
is the emitted concentration of the i-th contaminant (mg/m3);
- ET:
-
is the exposure time (hour/day);
- EF:
-
is the exposure frequency (day/year);
- ED:
-
is the exposure duration (years);
- heterogeneous reactions AT:
-
is the average time of exposure in a lifetime.
The non-cancer risk from the inhalation of the i-th contaminant, namely the hazard index (HII), was calculated as follows:
$$ {\mathrm{HI}}_{\mathrm{I}}=\frac{{\mathrm{EC}}_{\mathrm{I}}}{\mathrm{RfC}} $$
(9)
where RfC is the inhalation reference concentration of the i-th contaminant (mg/m3).
The RfC values, defined as an estimate of a concentration under continuous exposure for individuals that does not present any risk of deleterious effects during a lifetime, were selected from international databases. For inorganic compounds, these values refer to the elemental metal or, if not available, to a metal compound that is likely to be produced during open burning, as highlighted in Table 5.
Table 5 Reference concentrations for inhalation of the contaminants of interest For each WEEE component, the total hazard index (HI) was obtained as the sum of the inhalation hazard index estimated for the single contaminants.
The comparative analysis of the HI of the selected WEEE components was referred to a normalized HI (DpHI), which was calculated as the ratio between the HI of the single component and the minor HI.